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Asymmetric Organo-Metal Catalysis
Asymmetric Organo-Metal Catalysis
Concepts, Principles, and Applications
Liu-Zhu Gong
Author All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Liu-Zhu Gong publisher do not warrant the information
University of Science and Technology of contained in these books, including this book,
China to be free of errors. Readers are advised to keep
Department of Chemistry in mind that statements, data, illustrations,
230026 Hefei procedural details or other items may
China inadvertently be inaccurate.
Cover Design: Wiley Library of Congress Card No.: applied for

Cover Image: © Valentin Valkov/Getty
Images British Library Cataloguing-in-Publication Data
A catalogue record for this book is available
from the British Library.
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the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed bibliographic
data are available on the Internet at
<http://dnb.d-nb.de>.
© 2022 WILEY-VCH GmbH, Boschstr. 12,

69469 Weinheim, Germany
All rights reserved (including those of

translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other
means – nor transmitted or translated into a
machine language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even when
not specifically marked as such, are not to be
considered unprotected by law.
Print ISBN: 978-3-527-34592-2

ePDF ISBN: 978-3-527-34596-0
ePub ISBN: 978-3-527-34594-6
oBook ISBN: 978-3-527-34593-9
Typesetting Straive, Chennai, India

Printing and Binding
Printed on acid-free paper
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface ix
1 Why Is Organo/Metal Combined Catalysis Necessary? 1

1.1 Introduction 1
1.2 Early Stage of Organo/Metal Combined Catalysis and General
Principles 3
1.3 Organo/Metal Cooperative Catalysis 7
1.3.1 Control of Stereochemistry 7
1.3.2 Cooperative Activation of Chemical Bonds 9
1.4 Organo/Metal Relay and Sequential Catalysis 11
1.5 Conclusion 16
References 16
2 Metal/Phase-Transfer Catalyst Combined Catalysis 19

2.1 Introduction 19
2.1.1 Early Racemic Examples: PTC and Transition Metal Co-catalyzed
Reactions 19
2.2 Asymmetric Metal/Phase-Transfer Catalyst Combined Catalysis 20
2.2.1 Combination of Cationic PTC and Transition Metal in Asymmetric
Catalysis 22
2.2.2 Combination of Anionic PTC and Transition Metal in Asymmetric
Catalysis 29
2.3 Conclusion 33
References 34
3 Enamine-Metal Combined Catalysis 39

3.1 Introduction: Combined Enamine Activation and Metal Catalysis 39
3.2 Catalytic Asymmetric α-Allylation of Carbonyls 39
3.2.1 Oxidative Addition-Initiated Allylic Alkylation 39
3.2.2 Metal Hydride-Initiated Allylic Alkylation 48
3.2.3 Lewis Acid-Mediated SN 1 or SN 2 Reaction 50
3.3 Catalytic Asymmetric Substitution 51
vi Contents
3.4 Catalytic Asymmetric α-Alkenylation, α-Arylation, and

α-Trifluoromethylation of Carbonyl Compounds 55
3.5 Asymmetric Addition to Alkynes by Cooperative Catalysis with π-Lewis
Acids 59
3.6 Catalytic Asymmetric Propargylic Substitution Reaction of Carbonyl
Compounds 61
3.7 Catalytic Asymmetric α-Oxidation of Aldehydes 63
3.8 Relay Catalysis 64
3.8.1 Catalytic Asymmetric Cross Dehydrogenative Coupling 64
3.8.2 Transformation of Olefins 68
3.9 Conclusion 70
References 71
4 Iminium and Metal Combined Catalysis 75

4.1 Introduction: Iminium Activation and Metal Combined Catalysis 75
4.2 Iminium Activation and Palladium Catalysis 76
4.2.1 Enantioselective Conjugate Addition Reaction 76
4.2.2 Asymmetric [3+2] Cycloaddition Via Ring-Opening Oxidative
Addition 77
4.2.3 Asymmetric Michael Addition and Carbocyclization Cascade 81
4.2.4 Asymmetric Oxidative Cascade Reaction 83
4.3 Iminium Activation and Coinage Metal Catalysis 83
4.4 Iminium Activation and Other Metal Catalysis 85
4.5 Conclusion 87
References 88
5 Brønsted Acid and Transition Metal Cooperative Catalysis 91

5.1 Introduction 91
5.2 Early Stage of Metal/Brønsted Acid Cooperative Catalysis 93
5.3 Metal Alkynylide-Mediated Transformations 93
5.4 π-Allyl-Metal-Mediated Transformation 95
5.5 Asymmetric Hydrogenation of C—N Double Bond 107
5.6 Metal Carbene-Mediated Transformations 110
5.7 π-Lewis Acid Mediated Transformations 116
5.8 Summary and Outlook 119
References 120
6 Metal-Brønsted Acid Relay Catalysis 125

6.1 Introduction 125
6.2 π-Lewis Acid-Chiral Brønsted Acid Relay Catalysis 125
6.2.1 Hydroamination-Initiated Cascade Reaction 127
6.2.2 Hydroalkoxylation Mediated Relay Catalysis 132
6.2.3 Hydrosiloxylation Mediated Relay Catalysis 136
6.2.4 Relay Catalysis Involving the Addition of Nitrone or Nitro Group to
Alkynes 138
Contents vii
6.2.5 Relay Catalysis Involving the Addition of Carbon Nucleophiles to

Alkynes 139
6.3 Metal/Brønsted Acid Relay Catalysis Involving Alkene Metathesis 141
6.4 Metal/Brønsted Acid Relay Catalysis Involving Alkene
Isomerization 144
6.5 Metal/Brønsted Acid Relay Catalysis Involving Hydrogenation 151
6.6 Palladium/Brønsted Acid Relay Catalytic Asymmetric Allylation of
Carbonyls 155
6.7 Metal/Brønsted Acid Relay Catalysis Involving Hydroformylation 157
6.8 Metal/Brønsted Acid Relay Catalysis Involving Metal Carbene
Formation 160
6.8.1 Cascade Metal Carbene Formation and Asymmetric Protonation 160
6.8.2 Multiple Cascade Reaction Initiated with Metal Carbene 165
6.9 Lewis Acid/Chiral Brønsted Acid Relay Catalysis 167
6.10 Miscellaneous 169
References 173
7 Lewis Base–Lewis Acid Cooperative Catalysis 179

7.1 Introduction: Combined Lewis Base and Lewis Acid Activations 179
7.1.1 Early Examples in Lewis Base–Lewis Acid Cooperative Catalysis 183
7.2 Asymmetric Reactions Driven by Tertiary Amine-Mediated Ammonium
Enolates 184
7.2.1 Asymmetric Baylis–Hillman Reactions 184
7.2.2 Asymmetric [2+2] Reactions 186
7.2.4 Asymmetric α-Functionalization of Carbonyl Compounds 196
7.3 Asymmetric Reactions Driven by NHC-Mediated Homoenolates 198
7.3.1 Asymmetric Annulation Reactions 201
7.3.2 Asymmetric β-Protonation Reactions 211
7.3.3 Asymmetric Kinetic Resolutions 215
7.4 Asymmetric Reactions Driven by NHC-Mediated Azolium
Enolates 216
7.5 Asymmetric Reactions Driven by Ammonium Salts 221
7.6 Asymmetric Reactions Driven by NHC-Mediated α,β-Unsaturated Acyl
Azoliums 225
7.6.2 Asymmetric Cascade Reactions 229
7.6.3 Asymmetric Kinetic Resolutions 231
7.7 Conclusion 235
References 235
8 Lewis Base-Transition Metal Cooperative Catalysis 241

8.2 Phosphine and Transition Metal Cooperative Catalysis 243
viii Contents
8.3 N-Heterocyclic Carbene and Transition Metal Cooperative

Catalysis 244
8.3.1 π-Allyl Metal Mediated Transformations 245
8.3.2 Alkynyl-metal Mediated Transformations 253
8.3.3 Metal-allenylidene Mediated Transformations 254
8.4 Tertiary Amine and Transition Metal Cooperative Catalysis 258
8.4.1 π-Allyl Metal Mediated Transformations 258
8.4.2 π-Benzyl-metal Mediated Transformations 263
8.4.3 Metal-allenylidene Mediated Transformations 265
8.4.4 Other Transition Metal Mediated Transformations 267
8.5 Conclusions 271
References 271
9 Chiral Organocatalyst Combined with Transition Metal Based

Photoredox Catalyst 277
9.2 Covalent-Based Organocatalytic Activation in Combination with
Transition Metal-Based Photoredox Catalyst 279
9.2.1 Chiral Amine/Photoredox Combined Catalysis 279
9.3 Photoredox-Mediated SOMO Catalysis 284
9.4 Nucleophilic Organocatalyst in Combination with Photoredox
Catalyst 288
9.5 Noncovalent-Based Organocatalytic Activation in Combination with
Transition Metal-Based Photoredox Catalyst 290
9.5.1 Chiral Phosphate/Photoredox Combined Catalysis 290
9.6 Asymmetric Ion-Pair/Photoredox Combined Catalysis 295
References 297
10 Applications in Organic Synthesis 301

10.2 Applications of Chiral Phosphoric Acid-Metal Cooperative
Catalysis 301
10.3 Application of Transition Metal Catalysis Combined with Secondary
Amine Catalysis 305
10.4 Application of Photocatalysis Combined with Organocatalysis 310
10.5 Application of Lewis Base–Lewis Acid Cooperative Catalysis 312
10.6 Application of Lewis Base–Transition Metal Relay Catalysis 316
10.7 Application of Metal-Brønsted Acid Relay Catalysis 316
10.8 Conclusion 320
References 320
Index 325
ix
Preface
The alarming thalidomide tragedy of the 1960s has immediately led to a worldwide
revisit of enantiomers in the medicinal chemistry and pharmaceutical industries, as
the biological systems would recognize each enantiomer for either targeted activ-
ity or inactivity or severe side effect. Of all the synthetic strategies developed to
distinguish enantiomers in the intervening years, the catalytic process induced by
a chiral molecule, namely asymmetric catalysis, is undoubtedly the most efficient
approach to access enantiomerically pure compounds. In this context, enzymatic
transformations are the most natural way, albeit with limited tolerance of reaction
conditions; transition metal complexes are of stably increasing importance and pop-
ularity in both fundamental research and industrial applications; organocatalysis
employs purely small organic molecules as the catalysts to offer a convenient and
green solution to asymmetric synthesis.
In the pursuit of ideal synthesis, many have experienced the shortage of effective
chiral catalysts in regards to bond activation or stereochemical control. So, instead of
de novo design and synthesis of new chiral catalysts, why don’t try catalysts blending:
Combined Catalysis? Incompatibilities notwithstanding, there are vast opportunities
in combining distinct catalysts in a single operation for improving reaction efficiency
or offering a unique solution to challenging transformations. This book focuses on
the concept of Organo/Metal Combined Catalysis, the proof of concept, and thor-
oughgoing discussions of the reactions achieved, as the number of publications on
this field has been increasing exponentially during the last decades. Organo/Metal
Combined Catalysis dates back to the early 2000s when a chiral organocatalyst was
exploited to activate the nucleophiles, thus controlling the stereoselectivity of an
allylic alkylation with π-allyl palladium species, in the most desirable cooperative
manner. Interestingly, one catalyst of a compatible catalytic system may serve as a
relay shuttle for other catalytic cycles to enable orthogonal bond-forming reactions,
which has been named as relay catalysis (also known as cascade, domino, or tan-
dem catalysis). Once the incompatibility issue between catalysts has developed, the
Organo/Metal Combined Catalysis fells into a category of sequential catalysis, a com-
promise relay catalysis featuring stepwise catalysts addition.
This book covers the whole array of organo/metal combined catalytic systems
achieved to date, including 10 chapters: general introduction (Chapter 1);
phase-transfer-catalyst and metals (Chapter 2); enamine and metals (Chapter 3);
x Preface
iminium and metals (Chapter 4); Brønsted acid and transition metal cooperative
catalysis (Chapter 5); Brønsted acid and metal relay catalysis (Chapter 6); Lewis base
and Lewis acid cooperative catalysis (Chapter 7); Lewis base and transition metal
cooperative catalysis (Chapter 8); chiral organocatalyst and transition metal-based
photoredox catalyst (Chapter 9); applications in total synthesis (Chapter 10). All
knowledgeable authors, Dr. Zhi-Yong Han, Dr. Jie Yu, Dr. Chang Guo, Dr. Jin Song,
Dr. Dian-Feng Chen, and Dr. Pu-Sheng Wang, have significantly contributed to
the development of Organo/Metal Combined Catalysis, and can provide invaluable
perspectives.
This book could serve as an excellent textbook for graduate students and a
great handbook for researchers and other practitioners at all levels of asymmetric
synthesis.
1
Why Is Organo/Metal Combined Catalysis Necessary?
1.1 Introduction
Molecular chirality has played an important role in a broad scope of fields, includ-
ing synthetic chemistry, drug discovery, biological system, and materials science and
will continue to exert a great impact on physical science. Such unparalleled signif-
icance of chirality leads to increasing demand for efficient asymmetric protocols to
build up chiral structures.
Chiral resolution is the oldest way to isolate optically pure chiral molecules
from the racemic form. Chiral pool- and auxiliary-induced asymmetric synthesis
has frequently been synthetic strategies of choice to create chiral elements in
organic synthesis [1]. Although chiral auxiliary-induced asymmetric synthesis
has been prevalently applied to the asymmetric synthesis of natural products and
pharmaceutically significant substances, and thus held the historical impact on
synthetic chemistry [2], the installation and removal of chiral auxiliary basically
require additional reaction steps to thereby attenuate the synthetic efficiency.
Asymmetric catalysis has globally been accepted as the most efficient concept to
stereoselectively build up molecular chirality. Since the advent of asymmetric cyclo-
propanation and hydrogenation catalyzed by chiral copper and rhodium complexes,
respectively [3, 4], asymmetric metal catalysis has continuously been the central
focus of asymmetric synthesis. The versatility and robustness of metals in the acti-
vation of a wide spectrum of chemical bonds, even those with high bond energy,
have rendered many families of asymmetric transformations to be accessed by either
Lewis acid or transition metal catalysis [5, 6].
The control of stereochemistry in asymmetric metal catalysis principally relies on
the chiral ligand and to a large degree on the ligand acceleration [7]. The stereochem-
ical control events involved in the transition metal catalysis might be one or some
of the typical elementary reactions including chiral ligand coordination, oxidative
addition, insertion, and reductive elimination. The oxidative addition occurs more
easily with an electronically richer and low-valent metal to increase the oxidation
state and coordination number of the metal center; therefore the ligand coordina-
tion facilitates this reaction. The global and long-standing interest in the design and
development of chiral ligands has culminated in the explosive appearance of priv-
ileged ligands [8], which actually propel the proliferation of elegant and practical
Asymmetric Organo-Metal Catalysis: Concepts, Principles, and Applications, First Edition. Liu-Zhu Gong.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
2 1 Why Is Organo/Metal Combined Catalysis Necessary?
X
H
L* H2 X –ML*n X H
M ML*n *Ln M
H M L*n
H H
H
(a) Oxidative addition Reductive elimination
R R
L* R–X R′ M′
M ML*n *Ln M *Ln M R R′
X R′
(b) Oxidative addition Reductive elimination
Figure 1.1 Transition metal-catalyzed reactions initiated with oxidative addition.

(a) Hydrogenation. (b) Cross coupling.
asymmetric processes commencing with the oxidative addition, for example, asym-
metric hydrogenation and cross-coupling reaction (Figure 1.1).
High-valent transition metals have also been found to enable a tremendous
number of organic reactions. In contrast to abundantly available chiral ligands
for asymmetric catalysis beginning with the oxidative addition, which undergoes
with low oxidation state metals, rather fewer chiral ligands are compatible with
high-valent metal catalysis and reactions undergoing under oxidation conditions to
pose a great challenge to the control of stereoselectivity. For example, although the
high-valent metal-catalyzed transformations commencing with nucleometallation
(Eq. (1), Figure 1.2), aryl and allylic C–H activation (Eqs. (2) and (3)), have been
well established, a very limited number of chiral ligands can enable highly enan-
tioselective variants, in particular, those using molecular oxygen as the terminal
oxidant [9]. So far, chiral Lewis acids are successful representatives among massive
asymmetric high-valent metal catalysis [10]. As such, a new concept to break the
conventional wisdom that relies on the chiral ligand to control the stereochemistry
of transition metal catalysis is greatly desirable.
Asymmetric organocatalysis represents an important tool, independent, and
conceptually distinct from metal catalysis, to build up molecular chirality [11, 12].
The typical principles in organocatalysis for the activation of chemical bonds cover
a broad scope of concepts, including amine catalysis by enamine raising highest
occupied molecular orbital (HOMO) and iminium lowering lowest unoccupied
molecular orbital (LUMO), Brønsted acid catalysis by hydrogen-bonding interaction
or protonation, NHC catalysis via umpolung of aldehyde, Lewis base catalysis by
nucleophilic addition to either carboxylic acid derivatives or electron-deficient
carbon–carbon double bonds to form reactive enolate or acylammonium species,
and phase transfer catalysis by using ammonium and phosphonium to form ion
pairs with anionic nucleophiles [13]. Such versatile principles in the activation
of chemical bonds and structural diversity of organocatalysts have enabled the
explosive appearance of fundamentally novel asymmetric reactions and processes
featured by environmentally benign, atom, and step economies. Nevertheless, the
1.2 Early Stage of Organo/Metal Combined Catalysis and General Principles 3
HX/[O]
Nu MX(n-2)
MXn Nu Nu Nu
–X Nu′
Nu (1)
MX(n-1) MX(n-2) Nu′
MXn Nu′
Reductive elimination
HX/[O]
MXn MX(n-2)
Nu
H MX(n-1) MX(n-1)
–HX Nu* (2)
Nu*
HX/[O]
H MX(n-1) Nu MX MX(n-2)
MXn (n-2) MX(n-1) Nu*
Nu or
R * or R
–HX R R R Nu* (3)
R
Nu
Figure 1.2 Representatives of high-valent metal catalysis.
complete dependence upon the interactions between a highly active functionality

and the organocatalyst (Table 1.1) poses the organocatalysis essential constraints to
activate relatively inactive chemical bonds and unfunctionalized substrates.
1.2 Early Stage of Organo/Metal Combined Catalysis

and General Principles
The combination of asymmetric organocatalysis and metal catalysis integrates the

catalytic activity of metals and organocatalysts, hence allows the simultaneous or
sequential occurrence of multiply bond-breaking and forming events in stereochem-
ical control to provide much more diverse ranges of concepts or principles capable of
enabling unconventional enantioselective transformations that are toughly accessed
by the individual catalyst [14]. Very early reports on the asymmetric organo/metal
combined catalysis describe a Pd-catalyzed asymmetric allylic alkylation of an imino
ester, in concert with chiral phase transfer catalysis [15]. Gong and coworkers found
that the use of a cinchona alkaloid-derived ammonium bromide 4a that Corey devel-
oped [16] as the chiral phase transfer catalyst, in combination with an achiral palla-
dium complex of triphenylphosphine, is able to enable the reaction to deliver 59% ee
[15]. Takemoto identified that the electron density of the trivalent phosphorus ligand
exerts considerable impact on the reaction performance and the highest enantiose-
lectivity of 94% ee was obtained with 4b that Lygo introduced [17] in the presence of
triphenyl phosphite ligand. In both the cases, the respective and synergistic action of
the palladium complex and chiral PTC on the allylic ester 1 and nucleophile 2 ren-
ders the reaction to proceed more efficiently via a transition state TS-1 and allows
the stereochemical control to be accessed by chiral phase transfer catalyst, alone
(Figure 1.3). This strategy indicates that the stereoselection of metal-catalyzed reac-
tions can be controlled without chiral ligand, instead, by a co-organocatalyst, thus
Table 1.1 Typical activation modes in organocatalysis (OC).
Concepts of OC Active intermediates Applicable substrates Reaction types
Enamine catalysis Enolizable aldehydes and Aldol reaction

N
ketones Mannich reaction
Michael addition
Iminium catalysis Enal and enones Michael addition

N Diels–Alder reaction
Friedel–Crafts reaction
Brønsted acid catalysis H H Aldehydes, ketones, and Reduction

*B X X B* imines, enal, and enones Friedel–Crafts reaction
or
Michael addition
NHC catalysis Aldehydes Annulation

HO X R3
Benzoin reaction
Stetter reaction
R N
R2
R1
Lewis base catalysis Ketene, acylhalides, [2+2] cyclization
O anhydride, and other [4+2] cyclization
R analogues
LB Kinetic resolution
Enals, enones, and [3+2] cycloaddition

O α,β-unsaturated esters Baylis–Hillman reaction
R LB
Phase transfer catalysis Acidic nucleophiles Alkylation
R4N C(R′)3 or R4P C(R′)3 Aldol reaction
Mannich reaction
Michael addition
1.2 Early Stage of Organo/Metal Combined Catalysis and General Principles 5
[Pd(allyl)Cl]2/L, tBuO C N Ph
Ph N CO2tBu 4a or 4b 2
OAc +
1 Base, Toluene, 0 °C Ph
Ph 2 3
Br
I
O N [Pd(allyl)Cl]2 MeO N [Pd(allyl)Cl]2

(1 mol%) (9 mol%)
PPh3 P(OPh)3
(2.5 mol%) (40 mol%)
N CsOH•H2O N 50% KOH (aq)
4a (10 mol%) 4b (10 mol%)
95%, 59% ee 82%, 94% ee
OtBu
Chiral PTC controls O L Pd activates the
the stereochemistry N Pd electrophiles by
N
of nucleophile L oxidative addition
Ph
Ph
TS-1
Figure 1.3 Pd and PTC cooperative catalysis.
OCO2Me O O L Pd
O n
Bu3P (100 mol%)
R R R
Pd(PPh3)4 (1 mol%)
t-BuOH, 60 °C Bu3P
6
5 TS-2
Figure 1.4 Pd and phosphine cooperative catalysis.
opens up a window to seek unconventional modes to address issues of the stereo-

chemical control encountered in the asymmetric metal catalysis.
The cooperative catalysis of transition metal and Lewis base was first showcased
by Krische and coworkers [18]. Tributylphosphine undergoes Rauhut–Currier
type addition [19] with the enone moiety of 5 to generate a transient enolate and
simultaneously, the palladium complex reacts with the allylic carbonate part to give
a π-allylpalladium species. A subsequent intramolecular substitution occurs via a
transition state TS-2, and followed by elimination of tributylphosphine, to yield the
final product 6 (Figure 1.4). The perfect integration of the Lewis base and palladium
catalysis offers a unique activation mode to make the reaction that is otherwise
unable to proceed possible.
The cooperative catalysis of Lewis base and Lewis acid to drive an asymmetric
[2+2] annulation of acetyl chloride 7 and imino esters 8 was reported by Lectka and
coworkers [20]. The chelation of indium triflate to the imino ester 8 enhances the
reactivity of the imine functionality. Thus, the nonmetal-coordinated zwitterionic
enolate Int-1 generated from the acetyl chloride 7 with BQ 10 and base 11 is able to
undergo an enantioselective Mannich-type reaction with an In(III) cocatalyst-bound
imino ester Int-2 to form an intermediate Int-3. Finally, an intramolecular amide
bond formation delivers β-lactams 9 and regenerates the catalyst (Figure 1.5).
OMe
O O N Ts Ts O
R + 10 (10 mol%), In(OTf)3(10 mol%) N
Cl N
EtO H 11, Toluene
7 EtO2C R
8 Up to 98%, 99% ee 9 N
10, OBz
11 In(OTf)3 10
(OTf)3
O BQ Ts BQ Me2N NMe2
In
+ O N Ts LnIn N O
R H
EtO H EtO2C R
Int-1
Int-2 Int-3 11
Figure 1.5 Lewis acid and Lewis base cooperative catalysis.
Pd(PPh3)4 (5 mol%)
O O
15 (30 mol%)
R
1 +
R
2 R OAc R
2
R
DMSO, RT N
13 1 H
12 R
14 15
Ar
Rh(COD)2OTf (4 mol%) O
O BIPHEP (4 mol%) Ph O
P
Ph N 19a(4 mol%) OH
+ H N O
DCE, H2 (1 atm), 40 °C HO H
18 Ar
16 17
19a, Ar = (i-Pr)3C6H2
O O Et
O 23 (10 mol%) R N
i
2
Ti(O Pr)4 (20 mol%) 1 N N
H + R R
i
PrOH (20 mol%), DBU
R 1
R CH2Cl2, 23 °C 2 Et
R
20 21 Up to 82%, 99% ee 22 BF4
23
Figure 1.6 Typical organo/metal combined catalysis in the early stage. Source: Modified
from Arndtsen and Gong [25].
In the same period, the enamine and palladium [21], Brønsted acids and tran-
sition metals [22, 23], NHC and metal complexes [24], and some other combined
catalyst systems were successively reported, providing unusual fundamental bond
activation modes that turn out to be versatile platforms to allow for the proliferation
of unprecedented transformations (Figure 1.6) [25].
Most organocatalysts contain heteroatoms, which basically coordinate to metal
catalysts to change the catalytic activity and to result in the “self-quenching” in some
cases. As a consequence, the compatibility of metals and organocatalysts turns out
to be the key to success in the organo/metal combined catalysis. On the other hand,
the synergistic effect among the components of the combined systems is actually
most desirable. Based on the activation modes and reaction pathway, the asymmet-
ric organocatalysis combined with metal catalysis generally consists of cooperative
catalysis, relay catalysis (also known as cascade, demino, and tandem catalysis), and
sequential catalysis as well (Figure 1.7) [26].
Cat a A + B P
A
A + B P
A′ Cat b Cat a Cat b
P Cat a
B′
C D
B
Cat b C + D Stage 1 Stage 2
Cat. b and reactant D are added

All reactants and catalysts are present from outset
after the first cycle is complete
(a) (b) (c)
Figure 1.7 Categories of asymmetric organocatalysis combined with metal catalysis.

(a) Cooperative catalysis. (b) Relay catalysis. (c) Sequential catalysis. Source: Chen et al. [26].
1.3 Organo/Metal Cooperative Catalysis

1.3.1 Control of Stereochemistry
Cooperative catalysis refers to a catalytic process, which is initiated via the simulta-
neous and respective activation of two or more substrates, functionalities, or chemi-
cal bonds enabled by two or more individual metal and organocatalysts (Figure 1.7a).
The cooperative catalysis actually provides more possibilities to control the stereo-
chemistry of an asymmetric transformation by tuning the chirality of each individual
catalyst. For example, if the metal only works efficiently for breaking or assembling
the chemical bonds, but is unable to control the stereochemistry by varying chiral
ligands, the chiral organocatalysis concepts can be adapted to conquer the stereo-
chemical control issue (Figure 1.8a). In case no appropriate organocatalysts are able
to efficiently induce the stereoselectivity, chiral metal complexes would stand in for
addressing the stereochemical issue while the organocatalyst solely acts to activate
M O*
A + B Metal (M)
A B C*
Organocat (O)*
(a)
M* O
+ Metal (M)*
A B A B C*
Organocat (O)
(b)
M* O*
+ Metal (M)*
A B A B C*
Organocat (O)*
(c)
Figure 1.8 Strategies of stereochemical control in cooperative catalysis. (a) Combine

achiral metal complex with chiral organocatalyst. (b) Combine chiral metal complex with
achiral organocatalyst. (c) Combine chiral metal complex with chiral organocatalyst. Source:
Han et al. [27].
Ph Ph
O
0.5 mol% AlEt3 N
O N N
0.5 mol% 26 NC OH
+ TMSCN
R1 R2 0.25 mol% 27 R1 R2 Br OH HO Br
24 Up to 94% ee 25
26
27
Figure 1.9 Chiral Lewis acid and achiral Lewis base cooperative catalysis. Source: Chen
et al. [28].
X
Pd(OAc)2 (7 mol%) OHC
OHC 30 (14 mol%), 31 (50 mol%)
MeO PPh2
MeO PPh2 Me
THF, 0 °C N
1,2 76%, 98% ee 1,2 H
29
28 30 31
Figure 1.10 Asymmetric allylation enabled by chiral palladium complex and achiral
amine. Source: Bihelovic et al. [29].
the substrates (Figure 1.8b). If neither of the concepts offers high stereoselectivity,
both chiral metal complex and chiral organocatalyst can be applied to synergistically
control the stereoselectivity (Figure 1.8c) [27].
The combination of achiral metal catalysts and chiral organocatalysts appeared
at the beginning of this field [15]. In the same period, one of the earliest examples
describing merging the chiral metal complex and achiral organocatalyst was intro-
duced by Feng and coworkers who identified that the combination of an aluminum
complex of chiral salen 26 and an N-oxide Lewis base 27 was able to afford a highly
efficient and enantioselective cyanosilylation of ketones 24 (Figure 1.9) [28].
Saicic and coworkers described the combined use of a chiral palladium complex
of (R)-Ph-MeOBiPHEP 30 and an achiral amine 31 to establish a highly enantiose-
lective intramolecular α-allylation of aldehydes 28 (Figure 1.10) [29].
A binary catalyst made up of a chiral phosphoric acid and an iridium complex 34
adorned with Noyori-diamine ligand allows a highly efficient asymmetric hydro-
genation of acyclic imines 32 to give chiral amine 33 in almost perfect levels of
enantioselectivity. In this case, the matched chirality between the chiral diamine
ligand of the iridium complex 34 and the chiral phosphoric acid (R)-19a offers high
stereoselectivity (Figure 1.11) [30].
i Ar
Ph Ph Pr
Ar O O O
Ar (R)-19a (1 mol%) HN i
N H2N N S Pr P
34 (1 mol%) Ir
RL RS X
O O OH
RL RS 20 bar H2 33
i
Pr
Toluene, 20 °C Ar
32
Up to 96%, 99% ee 34: H–X = (R)-19a 19a, Ar = 2,4,6-(iPr)3C6H2
Figure 1.11 Asymmetric hydrogenation enabled by chiral iridium complex and phosphoric
acid. Source: Modified from Li et al. [30].
O OH [Ir(cod)Cl]2(2 mol%)
Ligand 38 (8 mol%) O Ph
Me + *
Ph *
39 (10 mol%), Cl3CCO2H H
Ph 36a Me Ph
DCE, 25 °C 37
35a
Up to 99% ee, 20 : 1 dr
O NH2 NH2
O
P N N N
P N
O O N
N
(R)-38 39a 39b

(S)-38
O H Ph O H Ph
O H Ph O H Ph
H H
H H
Me Ph Me Ph
Me Ph Me Ph
(S,R)-37 (S,S)-37 (R,R)-37 (R,S)-37
80%, >99% ee, 20 : 1 dr 71%, >99% ee, >20 : 1 dr 77%, >99% ee, >20 : 1 dr 78%, >99% ee, 15 : 1 dr
With (R)-38, 39b With (S)-38, 39b With (R)-38, 39a With (S)-38, 39a
Figure 1.12 Stereodivergent cooperative catalysis. Source: Modified from Krautwald

et al. [31].
In the cases of combining chiral metal and chiral organocatalysts, if both of them
are robust enough to control the stereochemistry, the cooperative catalysis will be
able to establish the stereodivergent construction of chiral structures by simply vary-
ing the stereochemistry of each individual chiral catalyst. The proof of concept in
this field was demonstrated by Carriera who first reported a stereodivergent allylic
alkylation between α-enolizable aldehyde 35a and an allylic alcohol 36a based on
the asymmetric cooperative catalysis of iridium complex of chiral phosphoramidite
38 and chiral primary amine 39, allowing access to four stereomers by altering the
stereochemistry of the chiral ligand and chiral amine (Figure 1.12) [31]. Afterward,
the cooperative catalysis of chiral rhodium complex and chiral amine, chiral iridium
complex and chiral Lewis base, as well as the iridium complex and chiral NHC car-
bene was successively discovered by different research groups for the establishment
of stereodivergent processes [32].
1.3.2 Cooperative Activation of Chemical Bonds

Simultaneous action of both the metal and organocatalyst on the same substrate
actually provides a unique tool to activate a chemical bond and thereby makes the
reaction that may not work upon, being promoted by either of individual catalysts
probably occur. The feasibility and robustness of this strategy have been implicit in
the activation of relatively inactive chemical bonds. For instance, both the allylic
C—N bond of allyl amines 40 and C—O bond of allylic alcohols 41 can be activated
by protonation as shown in Int-4 and hydrogen-bonding interaction as shown
in Int-5 with the chiral phosphoric acid, respectively, to facilitate the oxidative
addition of the palladium complex to give the π-allylpalladium phosphate complex
intermediate, which smoothly undergoes the enantioselective substitution reaction
with the enamine Int-6 via a transition state TS-4 to give α-allylic aldehydes 42
(Figure 1.13) [33]. It is worthy to mention that neither the allyl amine nor the allylic
Ph
Ph N R3 HO R3 Ar
H 1
41 CHO
R
3 CHO 40 R R
3
O O
R R
2 1
R2 CHO (S)-19a (3 mol%)
(R)-19a (1.5 mol%) R1 R2 P
42 42 OH
Pd(PPh3)4 (3 mol%) 35 Pd(PPh3)4 (1.5 mol%) O
Up to 89%, 97% ee Up to 98%, 99% ee
5 Å MS, MTBE, 40 °C Ph 2 CHNH 2 (40 mol%) Ar
Then 2 N HCl 5 Å MS, Toluene, 40 °C (S)-19a, Ar = (i-Pr)3C6H2
Then 2 N HCl
R3
*RO OR* H O
Ph P OR*
O O O P
Ph 3 Ph
R H O OR*
N H
R3 O OR* Pd(PPh3)4 Pd H
N Ph
Pd(PPh3)4 Int-5
1 P
R O OR* R1 1
H Ph
R
2 R N
2
Int-4 R Ph
TS-4 R2 Int-6
Figure 1.13 Allylation of aldehydes by cooperative catalysis of Pd, chiral Brønsted acid,
and amine. Source: Mukherjee et al. [33].
(R)-19a (3 mol%)
Pd(PPh3)4 (3 mol%)
PhC(CH3)2NH2 (60 mol%)
R1 2,6-DMBQ (150 mol%) CHO
+ R3
R3
R2 CHO 3 Å MS, MTBE, 60 °C R2 R1
43
Then 2 N HCl 42
35
Up to 90%, 95% ee
H *RO OR*
R1 Me P
N 3 O O
R Me
H OR* Ph Ph
LnPd/19a R3 R2 Me Pd H
O P OR* Int-8 N Me
Pd
R3 O R1
2,5-DMBQ L
43 n
Int-7 R2
TS-4′
Figure 1.14 Asymmetric allylic C–H functionalization by cooperative catalysis.
alcohol can undergo the oxidative addition without the assistance of the Brønsted
acid [34].
Even more remarkably, the Brønsted acid can facilitate the palladium-mediated
allylic C–H cleavage. Thus, the combination of the palladium complex, chiral
Brønsted acid, and primary amine allows an enantioselective oxidative α-allylation
of aldehydes 35 with α-olefins 43 [35]. The Pd-mediated allylic C–H oxidation gener-
ates the π-allylpalladium phosphate complex Int-7 that undergoes asymmetric ally-
lation with enamine Int-8 via the transition state TS-4′ similar to List’s model TS-4
to smoothly give the chiral aldehydes 42 in excellent enantioselectivity (Figure 1.14).
Adoption of visible light photocatalysis to combine with chiral organocatalysis
leads to another versatile concept for the development of asymmetric transforma-
tions that are unable to work based on traditional bond-activation and assembly
strategies [36]. MacMillan and coworker first described the integration of a photocat-
alyst 48 and a chiral amine catalyst 47a to establish an efficient α-alkylation of alde-
hydes 44 with α-bromocarbonyls 45 (Figure 1.15) [37]. Subsequently, merging the
O 0.5 mol% 48 O O Me N N
2
1 R 20 mol% 47a 2
R N HOTf
R + Br
H H N Ru N
44 O 2,6-lutidine, DMF
R1 O Me N tBu
45 fluorecent light, RT H N N
46
47a
48
Figure 1.15 Asymmetric organocatalysis combined with photocatalysis. Source: Modified

from Nicewicz and MacMillan [37].
ruthenium(II) or iridium(III) visible photocatalysts and chiral Brønsted acids [38],

NHC carbene [39], or other organocatalysts [40] were disclosed to promote asym-
metric transformations that proceed via transient radical intermediates in excellent
stereochemical control.
The organo/metal combined catalysts aforementioned are typical representatives
in the field of hybrid cooperative catalysis. Each of them consists of a large family
of chiral catalyst systems that provide plentiful synergistic activation of chemical
bonds and many possibilities to induce the stereoselectivity, allowing for the cre-
ation of new asymmetric transformations. A detailed description of this field will be
presented in Chapters 2–9.
1.4 Organo/Metal Relay and Sequential Catalysis

Relay catalysis is defined as a cascade process in which two or more sequential
bond-forming events are independently promoted by two or more catalysts in a cas-
cade manner. Based on the substrates, either the linear ligation (Figure 1.16a) or
annulation (Figure 1.16b) can be accessed by this catalytic strategy.
The sequential catalysis generally describes a one-pot reaction promoted by
different catalysts, which are chemically incompatible, and therefore parts of the
catalysts or, in some cases, reagents must be added after the previous catalytic
reaction is complete (Figure 1.7c) [26]. Both relay and sequential catalysis can
provide general platforms to design new protocols for the enantioselective con-
struction of molecular complexity from readily available starting materials, featured
by avoiding the additional workup of either isolable or transient intermediates to
thereby reduce labor, save time, and minimize waste. This book will be focusing
on discussion of cooperative and relay catalysis, both of which are chemically
compatible. Thus, sequential catalytic processes that proceed based on artificial
operation, will be excluded from this book except the very original ones that have
inspired the following developments.
Rovis coined the name of relay catalysis defining a cascade reaction constituted
of elementary steps promoted by the individual catalyst, respectively, and reported a
nucleophilic carbene and HOAt (53) relay catalysis for an amidation of α-reducible
aldehydes 49 and amines 50 to produce α-reduced amides 51 [41]. The aldehyde
49 undergoes a redox reaction with carbene to yield an acyl azolium Int-8, which
then condenses with 53 to give an even more reactive intermediate Int-9 capable of
participating in the subsequent amidation reaction (Figure 1.17).
Metal (M)
A + B + C D*
Organocat (O)
M (or O)
M (O) C O* (M*)
A B E E C
O* (or M*)
(a)
H S
R X Metal (M) R X
FG + S FG
Organocat (O)
M (or O)
H M (O) R S R S O (M)
S X FG O (or M) X FG
R X FG
(b)
Figure 1.16 General principal of organo/metal relay catalysis. (a) Intermolecular relay
catalysis. (b) Relay catalysis for annulation. Source: Han et al. [27].
O 20 mol% 52 O
H R1 20 mol% 53 R1 N
Ph H + N Ph N
Cl Cl R2 Et3N, tBuOH, THF N N C F
Cl R2 6 5
49 50 51 BF4
–
53 52
52, Et3N N
N N C F 50 N
6 5
O O N N N
53
N N
Ph N
Ph O OH
Cl N N 53
Cl
C6F5
Int-9
Int-8
Figure 1.17 Proof of concept of relay catalysis.
One of the earliest organo/metal relay catalysis describes cascade hydroformyla-

tion and asymmetric aldol reaction (Figure 1.18). The styrene derivatives 54 prefer
to undergo branch-selective hydroformylation catalyzed by rhodium complex of 57
to generate α-branched aldehydes, which then undergo a proline-catalyzed asym-
metric direct aldol reaction to give β-hydroxyketones 56. In contrast, α-alkenes 58
favorably undergo the linear-selective hydroformylation to give enolizable aldehy-
des, which then participate in the subsequent proline-catalyzed cross-aldol reaction
with another aldehyde 59 [42].
tBu
Rh(acac)(CO)2 (0.5 mol%) tBu
57 (2 mol%) O O
O L–proline (30 mol%)
OH O O P P O OMe
Ar + Ar
MeO O O
CO/H2 (1: 1), 40 °C
54 55 56 tBu t
Bu
Up to 89%, 1.5 : 1 dr, 77/ 99% ee
OMe
(a) MeO 57
(1) Rh(acac)(CO)2(0.25-0.5 mol%)

61 (1–1.8 mol%)
H2/CO(1 : 1), DMF OH
O L-proline (5 mol%)
R + HO R′
O N PPh2
R′ H (2) NaBH4, MeOH, 0 °C H
R = Alkyl 59 R
Up to 91%, 9 : 1 dr, 99% ee 60 61
58
(b)
Figure 1.18 Relay catalytic cascade hydroformylation and aldol reaction. (a) Eilbracht’s
work. (b) Breit’s work.
OMe
OMe
H [RuClH(CO)(PPh3) (1 mol%) Ph
N + MeO
R 65 (5 mol%), Toluene, 40 °C
62 NHR O O
MeO OMe OMe P
63 64 O OH
Ru–H
+
B Ph
H H
B–H 63 65 65
N N
R R
66 Int-10
Figure 1.19 Ru/Brønsted relay catalysis. Source: Modified from Sorimachi and Terada [43].
Terada and coworker established a one-pot tandem isomerization/carbon–carbon

bond-forming sequence of allylamines 62 and 63 enabled by the relay catalysis of a
ruthenium complex and Brønsted acid 65. The readily available allylamines 62 ini-
tially undergoes a double-bond migration catalyzed by ruthenium complex to give
an enamine 66, which then participates in a Brønsted acid-catalyzed addition reac-
tion with 1,3,5-trimethoxybenzene (63) via the intermediate Int-10 to yield 64 and
regenerate phosphoric acid 65 (Figure 1.19) [43].
Soon after these events, hydroamination of alkynes and asymmetric transfer
hydrogenation cascade processes, enabling the direct transformation of a linear
functionality, the carbon–carbon triple bond, to a stereogenic center, were estab-
lished by relay catalysis of gold complex and chiral phosphoric acid [44]. Gong
and coworkers elaborated a gold complex/chiral phosphoric acid relay catalytic
transformation to directly convert the propargylic anilines 67 to a number of chiral
tetrahydroquinolines 69 in excellent yields and with high levels of enantioselectivity
(Figure 1.20a) [44]. Coincidently, Liu and Che also found a cascade intermolec-
ular hydroamination and transfer hydrogenation reaction of alkynes 71 and
anilines 72 rendered by gold and chiral phosphoric acid relay catalysis to furnish
chiral secondary amine products 73 in excellent yields and enantioselectivities
(Figure 1.20b) [44].
EtO2C CO2Et Ph3PAuMe (5 mol%) Ar

+ 19b(15 mol%)
R
NH2 N Toluene, 25 °C, 16 h O O
H N R
67 Up to >99% ee H P
68 OH
69 O
Au(I) B*-H catalyzed Ar
asymmetric reduction 68
19b, Ar = 9-phenanthrenyl
Au(I)
Gold catalyzed
hydroamination 19b
R N R
NH2 N R
H Ar
Int-11 70 *B H
(a) Int-12 O O
P
JohnPhosAuOTf (1–2 mol%) R2 OH
(S)-19a(5–10 mol%) HN O
1 + 2
R R NH2
68, 5 Å MS, Benzene R1 Ar
71 72 40–60 °C 73 19a, Ar = 2,4,6-(i-Pr)3C6H2
Up to 98%, 96% ee
(b)
Figure 1.20 Gold/chiral Brønsted acid relay catalysis. Source: Modified from Liu and
Che [40].
Dixon combined a gold(I)-catalyzed intramolecular hydroalkoxylation of

3-butylnoic acids 74 to generate furan-2(3H)-one intermediates 77, a chiral phos-
phoric acid-mediated condensation with tryptamine 75 to form N-acyliminium
phosphate Int-13, and N-acyliminium cyclization, to accomplish a one-pot process
enabling the direct transformation of the 3-butylnoic acids 74 and the tryptamine
75 into chiral N-heterocyclic compounds 76 in great yields and stereoselectivities
(Figure 1.21) [45].
In the same year, You and coworkers reported a relay catalytic cascade
cross-metathesis and asymmetric Friedel–Crafts alkylation between indole deriva-
tives 78 and unsaturated carbonyls 79 [46]. The presence of the Grubbs catalyst is
sufficient to drive cascade reaction but in the racemic version [47]. The addition of
the chiral phosphoric acid 19a as co-catalyst allows the Friedel–Crafts alkylation to
proceed much faster and thus offers high stereoselectivity (Figure 1.22).
The earliest combination of iminium activation mode and transition metal for
sequential catalysis was described by MacMillan et al. The Grubbs II catalyst 81b,
Ph3PAuCl (0.5 mol%)

AgOTf (0.5 mol%)
CO2H NH2 Toluene, RT, 1 h O
N
+ Ar
Then 75, 19c (10 mol%) N R
N 80 °C 24 h H O
H O
75 Then 110 °C 24 h 76
R 74 P
Up to 96%, 95% ee
O OH
B* O Ar
Au(I) O O N
75 19c (B*–H)
R1
Au(I)-catalyzed 19c R Ar = triphenylsily
N
cycloisomerization 77 HInt-13
N-Acyliminium cyclization
Figure 1.21 Gold/chiral Brønsted acid sequential catalysis. Source: Modified from Yang
et al. [45].
O
MesN NMes
(S)-19a(5 mol%) R2 Cl
X R 2 81a(5 mol%) Ru
+ Cl
N O Toluene, 60 °C X O SO2NMe2
64–97% yield N
R1 79
78, X = O, NBoc
80–94% ee R1
80
81a
Figure 1.22 Relay catalytic cascade metathesis and Friedel–Crafts reaction.
O
O O
O O Me
+ + (1) 1 mol% 81b, 40 °C
H Me
82 83 OTMS (2) 20 mol% 47b, –50°C H
84 85 O
81b
is
atalys
O Iminium c
47b, 30 mol% proline
Me RT
H
86 O
HO Me
O O Me
O Me
Mes N N Mes
N Me Me
Cl
Ru H OH
Cl Ph N O H OH
Ph H H
PCy3
81b 47b (–)-Aromadendranediol 87
Figure 1.23 Sequential metathesis/Michael addition/aldol reaction. Source: Modified from

Simmons et al. [48].
5-hexene-2-one 82, and crotonaldehyde 83 are combined at 40 ∘ C to undergo the

metathesis to give a keto-enol 86. The subsequent asymmetric Michael addition of
∘
trimethylsilyloxyfuran 84–86 catalyzed by imidazolidinone 47b proceeds at −50 C
to generate 85. Finally, the intramolecular aldol reaction of 85 catalyzed by L-proline
allows the production of 87 in overall 64% yield and with 5/1 dr and 95% ee. This
sequential one-pot process enabled by the triple catalysis provides the key interme-
diate 87 to access natural product (−)-aromadendranediol (Figure 1.23) [48].
As aforementioned and also implied in the working models of organocatalysis
(Table 1.1), it is basically hard for organocatalysis to activate relatively inert chemical
bonds. For example, hydrogen is highly inert for pure organocatalysts and unable to
participate in the organocatalytic process. However, the adoption of transition metal
catalysis in the relay catalytic process can allow asymmetric hydrogenation to occur
by using the chiral organocatalyst to control the stereochemistry. Zhou and cowork-
ers combined chiral ruthenium complex and chiral Brønsted acid to establish highly
enantioselective hydrogenation of quinoxalines [49]. The Ru(II)-catalyzed hydro-
genation of quinoxaline 88 initially proceeds to generate dihydroquinoxaline 90,
which undergoes either a Ru(II)-catalyzed non-enantioselective hydrogenation or
a chiral phosphoric acid (S)-19a-catalyzed asymmetric disproportionation to give 89
(Figure 1.24). Since the chiral phosphoric acid-catalyzed self-transfer hydrogenation
H
N [Ru(p-Cymene)I2]2 (0.5 mol%) N Ar
(S)-19a(1.2 mol%) (9-anthryl)
O O
N Ar N Ar
H2(600 psi), Benzene, RT, 48 h H P
88 low 89
Up to 96% eeH ,2 s O OH
, H
H u]
N [R Ar
[Ru], H2 (S)-19a
2
Disproportionation (S)-19a, Ar = 2,4,6-(i-Pr)3C6H2
N Ar (Self-transfer
90 hydrogenation)
Figure 1.24 Relay catalytic hydrogenation.
is much faster than the Ru-catalyzed process, high levels of enantioselectivity are
achieved for the entire relay catalytic hydrogenation reaction.
The relay catalytic systems listed before are typical representatives and actually
provide the general reaction modes that are amenable to design new cascade pro-
cesses. Since these events, hybrid multi-catalyst relay catalysis has gradually been
blooming. Increasing attention has been paid to this field, leading to a large num-
ber of nonclassical asymmetric cascade transformations that will be highlighted and
discussed in detail in the next chapters, in particular in Chapters 3, 4, and 6.
1.5 Conclusion
Since the advent of asymmetric metal catalysis, the incorporation of chiral ligands
to the central metal has dominantly been the reliable strategy to address the stere-
oselective issue encountered in catalytic asymmetric reactions. The organo/metal
combined catalysis changes and even actually refutes such conventional wisdom.
The preponderance of activation modes and stereochemical options allocates unpar-
alleled capacity to the organo/metal cooperative catalysis for the creation of asym-
metric reactions. The sequential occurrence of multiply bond-breaking and forming
events in stereoselective manner featured in relay catalysis propels the emergence
of nonclassical cascade reactions. The last decades have indeed witnessed exciting
progress in asymmetric organocatalysis combined with metal catalysis. It is not to
overstate that the organo/metal combined catalysis is gradually altering the status
quo of asymmetric catalysis, to some degree, and will continue to exert an essential
impact on asymmetric catalysis.
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19
Metal/Phase-Transfer Catalyst Combined Catalysis
2.1 Introduction
Phase-transfer catalysis (PTC) has been recognized as one of the most useful
methodologies in both academia and industry, as it features mild reaction condi-
tions, simple procedures, low cost, environmentally benign reagents and solvents,
and the practicability for large-scale synthesis [1–4]. In general, PTC accelerates
a reaction by facilitating the migration of a reactant from one phase into another
where the reaction occurs. As a simple and classic example of PTC, the reaction of
1-chlorooctane and aqueous sodium cyanide is shown in Scheme 2.1 [3]. Although
heating the reaction mixture under reflux with vigorously stirring for one or two
days gives no apparent product, the addition of a catalytic amount of phosphonium
salt drastically accelerates the reaction to complete in several hours. In the catalytic
process, phosphonium cation not only transfers the cyanide anion into the organic
phase but also increases the nucleophilicity of the CN− due to the large ionic radius
of Q+ , which reduces the electrostatic interaction between the ion pair. Employing
chiral ammonium or phosphonium salts allows for enantioselective transfor-
mations, including the industrial synthesis of amino acids via the asymmetric
alkylation of glycine iminoesters with a chiral phase-transfer catalyst [5, 6].
Transition metal catalysts are crucial for modern chemistry considering their enor-
mous diversity in lowering the activation barrier for chemical reactions and the huge
number of reactions catalyzed by transition metal compounds. The combination of
transition metal catalysis and PTC offers more opportunities and advantages com-
pared to conventional catalytic strategies. In this chapter, we will briefly introduce
the early stage of transition metal/PTC combined catalysis and focus on the asym-
metric transformations enabled by the binary catalyst system.
2.1.1 Early Racemic Examples: PTC and Transition Metal Co-catalyzed

Reactions
One of the great challenges in catalysis is to integrate the advantages of
heterogeneous and homogeneous catalysis. The former features high efficiency,
easy separation of the catalyst from the product, but normally suffers from unsatis-
factory selectivity. The latter usually represents high selectivity and mild reaction
Asymmetric Organo-Metal Catalysis: Concepts, Principles, and Applications, First Edition. Liu-Zhu Gong.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
20 2 Metal/Phase-Transfer Catalyst Combined Catalysis
Bu3P+ (CH2)15MeBr– (1.5 mol%)

C8H17Cl C8H17CN
NaCN, H2O, 105 °C, 1.8 h
1 2
C8H17Cl + C8H17CN +
Q CN Q Cl (Organic phase)
SN2
(Interface)
NaCl + NaCN + (Aqueous phase)

Q CN Q Cl
Fast
Q : R4 N , R4 P
Scheme 2.1 Example of phase-transfer catalysis. MTBE, methyl tert-butyl ether; DCM,
dichloromethane; TBAB, tetrabutylammonium bromide. Source: Modified from Starks [3].
conditions, but catalyst and product exist in the same phase and difficult to separate.
In principle, a two-phase system might allow for good separation and integrates
advantages of heterogeneous and homogeneous catalysis.
Initial attempts of applying PTC to transition metal-catalyzed reactions appeared
in the 1970s. Alper [7] and Cassar [8] independently reported the catalytic carbony-
lation of benzyl bromide performed in a liquid–liquid biphase system and cooper-
atively catalyzed by a cobalt carbonyl and benzyltriethylammonium chloride. The
reaction is believed to proceed following the sequence in Scheme 2.2. Cobalt tetracar-
bonyl anion Int-1 is generated from dicobalt octacarbonyl and sodium hydroxide
and transported into the organic phase by forming a lipophilic intermediate Int-2
with the phase-transfer catalyst [9]. The reaction of the anion Int-1 with benzyl bro-
mide 3 gives an intermediate Int-3, which undergoes a ligand migration to form the
acyl complex Int-4 and a subsequent clearage of the cobalt carbon bond would afford
the carboxylate anion 4 in the aqueous phase. The overall reaction features very
mild conditions and a convenient work-up procedure. Besides carbonylation reac-
tions, hydrogenation, coupling, and other reactions enabled by transition metal/PTC
cooperative catalysis have also been reported [10–13].
2.2 Asymmetric Metal/Phase-Transfer Catalyst

Combined Catalysis
The combination of PTC and transition metal catalysis offers more options and addi-
tional stereocontrol strategies in asymmetric catalysis considering that either or both
of them can be chiral to impart asymmetric induction individually or synergistically.
Depending on the type of phase-transfer catalyst employed, the PTC and metal com-
bined catalysis can be categorized into metal and cationic PTC cooperative catalysis,
metal and anionic PTC relay catalysis, PTC combined with reactive metallic anions,
and metal combined with onium ligands (Scheme 2.3). In the metal and cationic PTC
Co2(CO)8 (2 mol%)
BnNEt3Cl (4 mol%)
ONa
Br CO (1 atm)
+ CO
NaOH (5 N) O
benzene, 25 °C
3 85% 4
O
NaOH Co2(CO)8
Ph
Q Br Q OH ONa OH
4
Aqueous phase Co(CO)4
Int-1
Interface
Ph Co(CO)4
Organic phase O
Int-4 Q Br
CO
Q Co(CO)4
Q Br + Ph Co(CO)4
Int-2
Int-3
Q : R4N
Ph Br 3
Scheme 2.2 Cobalt/PTC co-catalyzed carbonylation of benzyl halides.
cooperative catalysis, the nucleophile can be transformed into the reactive ion pair
Nu− Q+ upon exposing to a PTC and a base, and then reacts with the other inter-
mediate, generated from a metal-catalyzed elementary reaction (Scheme 2.3a). In
the metal and anionic PTC relay catalysis, a chiral anion is typically employed to
transfer the insoluble substrate into the solution as a chiral ion pair, which then par-
ticipates in a metal-catalyzed process to form the final product (Scheme 2.3b). It is
feasible to harness either chiral transition metal catalyst or chiral PTC to control the
stereochemistry of these reactions. If two types of chiral catalysts are employed, the
additional stereocontrol element is provided for the reaction, and thus a matched or
mismatched effect should be observed. In the third model, the PTC catalyst is used to
transfer a reactive metallic anion, such as permanganate, generating a chiral ion-pair
complex (Scheme 2.3c). The last strategy applies chiral bifunctional ligands bearing
onium ion moieties for metal-catalyzed transformations (Scheme 2.3d). Besides chi-
ral skeletons, these bifunctional ligands could also utilize external chiral counter
anions to control stereochemistry. In nature, the validity of the last two combined
catalysis concepts relies on the chiral ion-paired complex to act as a real catalyst
(Scheme 2.3c,d). In this regard, these strategies could also be considered as sole cat-
alyst promotion. As such, these two concepts will be mentioned very briefly at the
end of this chapter.
Metal
A A M
B* Metal
A Nu A X A B* P
Base
Q
Nu-H Nu Q Anionic PTC
(a) (b)
*
Q* + MX n Q* MX n L Q L Q
M X X*
Metallic Chiral ion pair, M
anions typically the ″real Chiral onium Onium ligand and
catalyst″ ligand chiral counter anion
(c) (d)
Scheme 2.3 Strategies of metal/PTC combined catalysis. (a) Metal/PTC combined catalysis.
(b) Metal/anionic PTC combined catalysis. (c) PTC and reactive metallic anions. (d) Metal
and onium ligand.
2.2.1 Combination of Cationic PTC and Transition Metal in Asymmetric

Catalysis
In 2001, the first examples of PTC/metal co-catalyzed asymmetric reaction was
established independently by Gong and Mi [14] and Takemoto’s group [15]. They
successively developed an enantioselective allylic alkylation of iminoesters 5 with
simple allyl esters 6 by the cooperative catalysis of chiral PTC and palladium
complex. Gong and Mi identified a cinchona alkaloid-derived ammonium bromide
PTC-1 as the chiral phase-transfer catalyst, in combination with an achiral palla-
dium complex of Ph3 P, to enable the reaction delivering 59% ee (Scheme 2.4). Either
(S)- or (R)-2,2′ -bis(diphenylphosphino)-1,1′ -binaphthyl (BINAP) was investigated
in combination with PTC-1 to reveal if the synergistic effect existed on the stereo-
chemical control. The use of (S)-BINAP as the ligand with PTC-1 gave the product
with only 20% ee and with the (R)-enantiomer predominating. In contrast, the
combination of (R)-BINAP with PTC-1 allowed the reaction to give 60% ee, but the
(S)-enantiomer predominated, the similar yield and ee were also obtained from the
reaction with PTC 1 in the presence of PPh3 . These results indicate that (S)-BINAP
and PTC-1 are mismatched but no synergistic stereochemical control occurs even if
the matched chiral ligand is used.
A significant improvement in the stereoselectivity of the Pd/chiral PTC cooper-
atively catalyzed allylic allylation of iminoesters was achieved by Takemoto and
coworkers (Scheme 2.5) [15]. The electron density of the trivalent phosphorus
ligand exerts a considerable impact on the reaction performance. Electronically
rich phosphine ligands, such as 1,2-bis(diphenylphosphino)ethane (DPPE) and
tributylphosphine, enable the reaction to give higher yield but lower enantiose-
lectivity than relatively electronically poor ones, such as triphenylphosphine and
triphenyl phosphite. In particular, the highest enantioselectivity was obtained in the
presence of triphenyl phosphite under identical conditions, albeit with the sacrifice
of the catalytic efficiency. Ultimately, the combination of the palladium complex
[Pd(allyl)Cl]2 (1 mol%) R2
PPh3 (2.5 mol%) R1
Ph R2 Ph
PTC-1 (10 mol%)
R1 OR
Ph N CO2t-Bu + CsOH•H2O Ph N CO2t-Bu
5 6 4 Å MS, toluene, 0 °C 7
34–93% yield
10–61% ee
Ligand effect: (S)-BINAP: 75% yield, 20% ee (R)
(R)-BINAP: 98% yield, 60% ee (S)
PPh3: 95% yield, 59% ee(S)
Scope of allyl esters: Br
OAc OBoc OCO2Et N

O
95% yield, 87% yield, 93% yield,
59% ee 10% ee 37% ee
N
OAc Ph OCO2Et Ph OAc PTC-1
92% yield, 75% yield, 64% yield,

47% ee 38% ee 55% ee
Scheme 2.4 Pd/chiral PTC catalyzed asymmetric allylation of iminoesters.
[Pd(allyl)Cl]2 (9 mol%)
P(OPh)3 (40 mol%) R
Ph Ph
PTC-2 (10 mol%)
+ R OAc
Ph N CO2tBu Ph N CO2tBu
50% KOH (aq)
5 6 toluene, 0 °C 7,R = H, Ar
39–89% yield
R = H, Ar
91–96% ee
Effect of the achiral phosphine ligand (using KOH solid as the base)
I
Entry Ligand (mol %) Yield (%) ee (%)
MeO N
1 DPPE (8) 74 24
2 n-Bu3P (16) 69 4
3 Ph3P (16) 32 59 N
4 19 82 PTC-2
(PhO)3 P (16)
Representative products:
Ph Ar Ar
Ph Ph Ph Ph
Ph N CO2tBu Ph N CO2tBu Ph N CO2tBu Ph N CO2tBu

7a 7b 7c, Ar = 4-Cl-C6H4 7d, Ar = 4-OMe-C6H4
82%, 94% ee 89%, 96% ee 89%, 96% ee 39%, 96% ee
Scheme 2.5 Asymmetric allylic allylation of iminoesters catalyzed by chiral PTC and
palladium complex of triphenyl phosphite.
of triphenyl phosphite and O-methyl chinconidinium PTC-2 appeared to be the

best catalyst system and delivered good yields and excellent enantioselectivities.
Employing 50% KOH in an aqueous solution to supercede KOH solid rendered the
reaction to offer higher enantioselectivity. In addition, the asymmetric allylation
reaction with racemic branched allyl ester 8 gave the same linear-selective product
with almost identical enantioselectivity (93% ee).
The palladium-catalyzed asymmetric allylic alkylation of racemic 8 was also inves-
tigated in presence of triphenyl phosphite and MOP, respectively, by using PTC-2 as
the co-catalyst (Scheme 2.6a) [16]. The palladium complex of triphenyl phosphite
favored the generation of linear product 7b but still gave considerable amounts of
branched selectivity. As Hayashi reported, the MeO–MOP was convinced to promote
an inner attack of nucleophiles to the π-allylpalladium(II) complex generated from
8, producing the terminal alkene 9 as the major product [17]. However, in contrast
to Hayashi’s observation, the use of MOP to replace triphenyl phosphite led to the
predominant generation of linear product 7b in 70% yield and with 90% ee, accom-
panying with small amounts of branched product 9 with 85% ee. From the mech-
anistic point of view, the π-allylpalladium(II) complex Int-5 couples with a chiral
ion pair formed from the iminoester 5 and PTC-2 to give product 7, stereoselectively
5
Pd2(dba)3 ⋅CHCl3 Ph Ph
ligand(L) Ph Ph
OAc PPh2
PTC-2 +
Ph N CO2tBu Ph N CO2tBu OMe
Ph toluene, 0 °C
7b 9
8
L = (PhO)3P: (29%, 89% ee) (11%, >95% de, 85% ee)
L = (R)-MeO-MOP: (71%, 90% ee) (13%, 90% de, 85% ee) (R)-MeO-MOP
(a)
R
R OAc
6 OAc 8
+ R R R
R
+X
+
Pd +L Pd Pd Pd
L L L X X L X L
Cationic complex (Int-6) Neutral complex (Int-5) Int-7 Int-8

(reactive) (reactive)
5 ⋅ metal 5 ⋅ Q*
5 ⋅ Q* Slow Fast
Achiral Chiral ion Chiral ion
enolate pair pair
R + R
(±)- 7 (S)-7 Nu Nu
Background ent-9 9
reaction
(b)
Scheme 2.6 Mechanism studies on the chiral PTC/Pd co-catalyzed asymmetric allylation
of iminoesters. Source: Modified from Nakoji et al. [16].
(Scheme 2.6b). The cationic π-allylpalladium complex is more reactive than the neu-
tral complex Int-5 [18]. In the cases involving more σ-donating ligands, such as
DPPE and n-Bu3 P, more active complex Int-6 might be formed dominantly, which
would be able to react with the achiral enolate and to give the racemic product. In
contrast, when the more π-accepting ligand such as (PhO)3 P is used, complex A is
formed exclusively and the racemic background reaction can be significantly inhib-
ited. On the other hand, the branched allyl ester 8 undergoes oxidative addition with
Pd to initially generate π-allylpalladium complexes Int-7 and Int-8, respectively. The
stronger trans influence of (PhO)3 P and MOP principally enables the nucleophilic
attack to favorably occur on the carbon trans to the ligand, yielding branched prod-
uct. However, the nucleophilic attack is still a rather slow process due to the severe
steric hindrance, and the π-allylpalladium complexes Int-7 and Int-8 could isomer-
ize rapidly to complex Int-5 via exchange of the coordination site of L and X, leading
to the formation of the linear product as the major product. Regardless of either path-
way via that the allylic alkylation event proceeds, the chiral ion pair generated from
5 and the PTC-2 can effectively control the stereochemistry to give the product 7b
or 9 with high stereoselectivity.
Although palladium catalyst prefers the linear-selective allylic alkylation prod-
uct, other transition metals, including Ir [19–22], Mo [23, 24], and W [25, 26] as
well tend to drive the allylic alkylation to occur at the more substituted terminus of
the allylic substrate to give the branched product. In 2003, Takemoto and cowork-
ers reported their endeavors to investigate the iridium complex/PTC cooperatively
catalyzed asymmetric allylic alkylation of iminoesters [27]. The combination PTC-2
and iridium complex of triphenyl phosphite exclusively provided the branched prod-
ucts 9′ and 9 even if the linear cinnamyl alcohol derived allyl esters were employed
as the substrates. However, the yield and stereoselectivity of 9′ remained moderate
regardless of alternating the leaving group of allylic substrate. On the other hand,
the use of bidentate chiral ligand L1, without the addition of PTC, considerably
enhanced the enantioselectivity of the major product to up to 97% ee (Scheme 2.7).
Umpolung [28] addition of imines, in which imines serve as nucleophiles, offers
a unique approach to chiral amines [29–31]. In 2015, Deng’s group successfully
realized the first asymmetric umpolung addition of imines with various Michael
acceptors using chiral ammonium salt PTC [32]. Inspired by this work, Han and
coworkers established an Ir/PTC cooperatively catalyzed asymmetric umpolung
allylic substitution of simple α-iminoesters with allyl acetates, providing facile
access to chiral α-quaternary amino acid derivatives bearing two vicinal stereo-
centers (Scheme 2.8) [33]. 1,1′ -bi-2-naphthol (BINOL)-based phosphite L1 with a
sulfur atom at the alkyl chain, developed by Takemoto’s group, proved to be the
optimal ligand for the reaction. The existence of a PTC as the co-catalyst was found
to be crucial for the reaction. Through a thorough screening of the PTC, including
a number of chiral PTCs such as PTC-4 and PTC-5, achiral tetrabutylammonium
bromide (PTC-3) was found to be the best option. Without the phase-transfer
catalyst, the yield of the reaction decreased severely, and diminished enantiose-
lectivity was observed. The reaction generally offers good yields, high diastereo-
and enantioselectivities employing aromatic allyl acetates. Alkyl allyl acetate,
5
[Ir(cod)Cl]2 (10 mol%) Ph
(PhO)3P (40 mol%) Ph Ph
Ph
Ph OX PTC-2 (10 mol%)
Ph N CO2tBu + Ph N CO2tBu
Toluene, 25 °C
6 9
Ph
Ph
X Yield (%) dr ee of Ph N CO2t-Bu
Ac (6a ) 31 77/23 49 7b, linear product

not observed
Bz (6b) 40 75/25 46
CO2Me (6c) 15 80/20 29

O
CO2Ph (6d) 23 83/17 57 P O
O
PO(OEt)2(6d) 47 83/17 26 EtS
L1
Scheme 2.7 Chiral PTC/achiral iridium co-catalyzed asymmetric allylation of iminoesters.
[Ir(cod)Cl]2 (5 mol%)
L1 (10 mol%) R O
NBn PTC-3 (10 mol%)
OtBu KOH (1.5 equiv) OtBu
Ar R OAc
H2N Ar
O Fluorobenzene
10 6 25 °C, 12–36 h, then workup 11
Up to 88% yield
Base [Ir] Up to >20 : 1 dr Workup
PTC Up to 96% ee
Ph Ph R O
R 4N [Ir]
N N R4N Asymmetric allylation OtBu
+ R′ N Ar
Ar CO2tBu Ar CO2tBu π-allyl complex
Int-9 Int-9´ Int-10 Ph 12
2-Azaallyl anions
H
H Br NO2
N O
O N
P O N
O Br OH Bn N N
H H
EtS N Br
L1 PTC-3: TBAB PTC-4 PTC-5
O O
MeO O
O OtBu + OtBu
OtBu H2N Ph
H2N Ph
OtBu H 2N
H2N Ph 11c 11c´
74% yield, b:l = 2 : 1,
11a 11b OMe b: 2 : 1 dr, 81% (70%) ee
61% yield, 93%(71%) ee 80% yield, 96% ee l: 8% ee
dr 4 : 1 dr >20 : 1
Scheme 2.8 Ir/PTC cooperatively catalyzed asymmetric umpolung allylic substitution of

simple α-iminoesters with allyl acetates. Source: Modified from Su et al. [33].
O R O R
[O]
O PdII Base
Nu
R
14 Pd(0)
Int-11 13
Nu
O OPdII
R R
PdII Int-12
Int-14
R
PdII
Int-13
Scheme 2.9 Pd(II)-mediated electrophilic vinylogous reaction.
(E)-pent-2-en-1-yl acetate, delivers the desired amino acid derivative with a 2 : 1 b:l
ratio and with high ee for the major product.
Stahl found that the enolizable ketone can undergo a Pd(II)-catalyzed dehydro-
genation to generate the corresponding α,β-enone by forming Pd(II)-enolate species
in the presence of a base and then undergoing the subsequent β-hydride elimination
[34]. Chen and coworkers proposed that a similar transmetalation between palla-
dium acetate and dienolate Int-11 generated from the deprotonation of allyl ketone
13 with a base gave an intermediate Int-12. The intermediate Int-12 then undergoes
1,3-Pd migration to form η1 -allyl palladium Int-13, which then tautomerizes into a
π-allyl palladium intermediate Int-14. The allylic substitution of the intermediate
Int-14 with a nucleophile would occur in a direct vinylogous umpolung manner to
yield 14 (Scheme 2.9).
Based on this mechanistic hypothesis, Chen and coworkers established a
highly enantioselective oxidative coupling between oxindoles 15 and allyl ketones
13 enabled by the cooperative catalysis of palladium acetate and chiral PTC
(Scheme 2.10) [35]. Either L-amino-acid-derived phosphonium salt PTC-6 or
PTC-7 was identified as the best co-catalyst to offer the highest enantioselectiv-
ity. A broad range of 3-substituted oxindoles underwent the reaction smoothly,
generally giving the multifunctional products bearing an all-carbon quaternary
stereocenter with excellent enantioselectivities. 3-Indolinone-2-carboxylic and
2-cyclopentanonecarboxylic esters were also suitable for the reaction, leading to
the products 16c and 16d with moderate and high enantioselectivities offered by
PTC-6 and PTC-7, respectively. Dienol silyl ether 18, holding similar reactivity to
the dienolate, is also able to undergo oxidative allylic alkylation reaction in lieu of
the allyl ketone 13 to provide 19 with excellent enantioselectivity. The chiral anion
pair Int-15 generated from 15 and the phase-transfer catalyst is believed to undergo
R2 R
Pd(OAc)2 (5 mol%) R2
O PTC-6 (10 mol%)
+ O
R1 O 1 O
R
N Na2CO3 (0.5 equiv), O2 R
N
13 H Toluene, –10°C H
15 16
H H
O N O N PAr3
*R O
Br Br R2
PAr3 PPh3 R
R1 O
F3C CF3 PdII
Ar Ar N
H Int-14
Ar = 3,5-(Me)2C6H3 Ar = 3,5-(Me)2C6H3 Int-15
PTC-6 PTC-7
Ph Ph O O
Ph Bn
CO2Me CO2tBu
O O COPh COPh
O * *
O
N N N
H H
H 16d
16a 16c 76%, 84% ee
16b
91%, 97% ee 61%, 72% ee using PTC-7
83%, 97% ee
OH
Ph (1) Pd(OAc)2 (30 mol%) Ph
PTC-6 (10 mol%)
+ OTMS
O O
Na2CO3 (1.0 equiv), O2
N N
Toluene, –10°C
Boc Boc
17 (2) NaBH4, DCM/MeOH 19
18 61%, 93% ee
Scheme 2.10 Asymmetric vinylogous umpolung reaction. Source: Modified from Ran
et al. [35].
the enantioselective coupling with the π-allyl palladium intermediate Int-14 to

yield the chiral products 16.
Either ammonium or phosphonium salt PTC-catalyzed enantioselective transfor-
mations usually utilize enolizable pronucleophiles under basic conditions and con-
trol the stereochemistry via chiral ion pairs. Only a limited number of examples
describe nonenolizable, but still stabilized anionic carbon nucleophiles in asymmet-
ric phase-transfer catalysis [36–39]. Recently, Maruoka and coworkers developed an
enantioselective alkynylation of isatin derivatives using chiral ammonium bromide
PTC-8 and silver acetate binary catalyst system (Scheme 2.11) [40]. The complexa-
tion of AgOAc and the chiral quaternary ammonium salt PTC-8 generates a chiral
ion pair 23, which can form a chiral silver alkynylide 24 with alkyne 20 in the pres-
ence of a base. The chiral ion pair 24 then reacts with isatin 21 to give 25, which
finally undergoes protonation to yield product 22.
AgOAc (5 mol%) R1
O PTC-8 (5 mol%) HO
K2CO3 (0.5 equiv)
R1 H + R1 O R2 O
N Mesitylene, 60 °C N
20 21 CPh3 Up to 97% ee
22 CPh3
K2CO3 AgOAc
Q* [Ag(OAc)Br] Q* Br
23 PTC-8
R1
Q* XAg O
R1 21
AgX Q*
R2 O
N
24 25
CPh3
Ar
Br
Ar
PTC-8(Ar = (3,5-(CF3)2C6H3)2C6H3)
Scheme 2.11 PTC/Ag(I) cooperatively catalyzed enantioselective alkynylation of isatin

derivatives.
2.2.2 Combination of Anionic PTC and Transition Metal in Asymmetric

Catalysis
In contrast to cationic PTC, anionic PTCs can transfer cations into the
reaction phase. As early as the 1980s, tetraphenylborate anion and its sderiva-
tives were identified to transfer cations in several reactions. For example,
tetrakis[3,5-bis(trifluoromethyl)phenyl] borate was reported to catalyze the
diazotization of anilines in a dichloromethane/aqueous sulfuric acid two-phase
system [41, 42]. The resulting diazonium group could further undergo one-pot
transformations, such as bromination and hydroxylation reactions. However,
the establishment of asymmetric anionic PTC did not have much success until
the 2010s [43]. In 2011, Toste reported an asymmetric electrophilic fluorination
reaction using an insoluble cationic electrophilic fluorination reagent (Selectfluor)
with BINOL-derived phosphate as the chiral anionic phase-transfer catalyst [44].
Since then, chiral anionic PTC has enabled a number of highly enantioselective
transformations [45–47].
Pd2(dba)3 (5 mol%)
CPA-1 (10 mol%)
28 (16 mol%) Ar
ArN2BF4 + + R
R B2pin2
27 Na3PO4, Et2O Bpin
26
Insoluble 29
Na3PO4 ≡
NaB* B*-H CPA–1 Transmetalation Base
Pre-catalyst reductive elimination
NaBF4 Pd(0)
B*
R β-H elimination R
Pd(0) 27 R PdLn B* reinsertion
ArN2 B* PdLn B*
Oxidative ArPdLnB* Insertion
Int-16 addition
Int-17 Ar Ar
Soluble chiral Int-18 Int-19
ion pair
Ar
Bpin O OMe O
O O
P F3C CF3
O
O OH
Ar
28
29a Ar = 2,4,6-(Cy)3C6H2
39%, 90% ee CPA-1
Bpin
Bpin O OMe Bpin CO2Et
CO2Et
O
MeO t
Bu
29b 29c 29d
58%, 87% ee 47%, 89% ee 33%, 98% ee
Scheme 2.12 Enantioselective 1,1-arylborylation of alkenes.
In 2015, Toste reported an enantioselective 1,1-arylborylation of alkenes rendered

by chiral anionic PTC and palladium cooperative catalysis (Scheme 2.12) [48]. By
employing chiral phosphoric acid (CPA)-1 to generate the anionic PTC and 28 as
a ligand for the palladium catalyst, a three-component reaction of aryl diazoniums
26, alkenes 27, and pinacol diborate provides chiral benzylic boronates 29 with high
to excellent enantioselectivities. In this reaction, the insoluble aryldiazonium salt
26 undergoes a metathesis reaction with sodium phosphate to provide soluble chi-
ral ion pair Int-16, which upon undergoing oxidative addition could generate Pd(II)
species Int-17 bearing a chiral counter anion. The complex Int-17 would undergo
alkene insertion to give a complex Int-18, which could be transformed into a com-
plex Int-19 through a β-H elimination/reinsertion sequence. After transmetalation
and reductive elimination, Int-19 could be converted into the chiral borons 29 and
release both catalysts.
Inspired by Toste’s work, Gong and coworkers developed a highly selective
multicomponent carbonyl allylation reaction of 1,3-butadienes, aryldiazonium
tetrafluoroborates, and aldehydes (Scheme 2.13) [49]. The Pd(II) complex Int-17,
generated from the oxidative addition of Pd(0) complex to the soluble chiral iron
32 (1.2 equiv)
Pd(OAc)2 (10 mol%)
O CPA-2 (10 mol%) HO
ArN2BF4 + R +
Ar
H R′ NaHCO3, toluene
30 R′ R
26 31 Up to 99% yield
Insoluble >20/1 Z/E
33
94% ee
Na3PO4
NaB* B*–H ≡ CPA-2
Pre-catalyst
NaBF4 R′CHO
Ln B*
Pd(0) 30 Pd 32 B(OR″) 2
ArN2 B* Oxidative ArPdLn B* Insertion Ar * Ar
addition R R
Int-16 Int-17 Int-20 Int-21
iPr iPr
Observed side product:
iPr
O Ph O O Ph OH
O Ph Ph B(OR″) 2
P B B R′CHO
O OH Ph O O Ph * R′
iPr Ph Ph R
R
32 Ar Ar
iPr
iPr Int-22 34
CPA-2
Scheme 2.13 Enantioselective multicomponent carbonyl allylation reaction of

1,3-butadienes, aryldiazonium tetrafluoroborates, and aldehydes.
pair Int-16, undergoes an insertion reaction with diene 30 to give a chiral π-allyl
Pd complex Int-20, which reacts with diboron 26 to give chiral allylboron Int-21.
Int-21 would undergo allylation reaction with aldehydes to give enantioenriched
homoallylic alcohol 33. A side product 34, probably generated from allylboron
Int-22, was also observed. The 1,1′ -spirobiindane-7,7′ -diol (SPINOL)-derived
phosphoric acid (CPA-2) offered the highest enantioselectivity and the use of bulky
diboron 32 was the key to inhibit the generation of 34 and provided almost perfect
Z/E selectivity [50].
By virtue of the similar strategy, the same group established an enantiose-
lective three-component carbonyl allylation reaction of 1,3-butadienes, alkynyl
bromides, and aldehydes to produce densely functionalized homoallylic alcohols
(Scheme 2.14) [51]. Chiral silver phosphate 37 was identified as the best anion PTC
and appeared to be slightly more effective for the stereocontrol than the corre-
sponding phosphoric acid. The combination of 37 and palladium acetate, together
with the presence of bulky diboron 32 allowed the multicomponent reaction to give
excellent Z/E- and enantioselectivity. In this process, the formation of the chiral
Pd(II) species Int-23 through a metathesis process driven by the precipitation of
AgBr is believed to be the key intermediate that is responsible for the stereocontrol
of the whole reaction. As such, the use of Ag2 CO3 is crucial for the reaction to
proceed and also for the regeneration of the anionic chiral PTC.
Toste and coworkers created an enantioselective 1,1-diarylation of acrylates
27 by means of Pd and anionic PTC cooperative catalysis (Scheme 2.15) [52].
The reaction proceeds through a pathway similar to the enantioselective alkene
32 (2 equiv)
Pd(OAc)2 (7.5 mol%)
Br 2
O 37 (15 mol%) R
Cy
+ + Ar
2 Ag2CO3 1 Cy
R H HO R
Ar 1 Toluene, 25 °C
R 36 Pd(0)
35 30 31 +
Cy
OR
31 examples, O
Up to 99% yield B* B O
Borylation P
>20/1, Z/E; 93% ee OR
allylaton OAg
Ag2CO3 O
Cy
Pd(0)
AgB*
Br Cy
AgB* B* B*
Ln Pd 30 Ln Cy
Ln Pd Pd Ar
Insertion 37, B*–Ag
Int-22 Int-23 R
Ar Ar Int-24
Scheme 2.14 Enantioselective three-component carbonyl allylation reaction of

1,3-butadienes, alkynyl bromides, and aldehydes.
Pd2(dba)3•CHCl3 (2 mol%)
O CPA-3 (4 mol%) O Ar
28 (16 mol%)
ArN2BF4 + + Ar′-B(OH)
RO 2 RO Ar′
26 NaHCO3, Et2O, 20 °C
27′′ 38 39
Insoluble Up to 96% ee
NaHCO3 Transmetalation Base

NaB* B*–H ≡ CPA-3 reductive elimination
Pre-catalyst Pd(0)
NaBF4 38 B*
Pd(0) 27′ LnPd B* β-H elimination B*

reinsertion
ArN2 B* Oxidative ArPdLn B* RO2C
Insertion RO2C
addition II
Int-16 Int-17 Int-25 Ar LnPd Int-26
C8H17 Ar
O O O O
Cl P
BnO O OH
O
OH OH
39b C8H17 Ar
39a Cl
47%, 75% ee 68%, 96% ee Ar = 9-Anthracenyl
CPA-3
Scheme 2.15 Enantioselective 1,1-diarylation of acrylates. Source: Modified from

Yamamoto et al. [52].
1,1-arylborylation reaction described by the same group [48]. After the aryl palla-
dium phosphate Int-17 undergoes a Heck-type insertion reaction with the acrylate
and followed by the β-elimination and reinsertion sequential process to generate a
key intermediate Int-26 stabilized as a π-benzyl species. The intermediate Int-26
undergoes transmetalation with arylboronic acid and reductive elimination to
generate 39. CPA-3 appeared to be the superior catalyst and allows the reaction to
give excellent enantioselectivity. However, the enantioselectivity is highly sensitive
to the electronic and steric nature as well as the position of substituents on the
2.3 Conclusion 33
benzyl acrylate substrate. The use of a multidimensional modeling technique to

investigate the effect of the chiral anionic phase-transfer (CAPT) catalyst and the
acrylate suggests that the attractive noncovalent interactions between the two
components are controlling elements in the enantiodetermining step.
The groups of Toste and Sunoj developed an asymmetric Heck–Matsuda reaction
of cyclic alkenes and aryl diazonium salts by taking advantage of palladium and
anionic PTC cooperative catalysis (Scheme 2.16) [53, 54]. The catalytic cycle includes
the formation of ion-pair Int-16 through the anion transfer process, oxidative addi-
tion with the Pd(0) catalyst to give aryl palladium species Int-17, migratory insertion
to the cyclic alkene followed by β-H elimination to afford the final product. For some
cyclic alkenes, a considerable amount of byproduct caused by double bond isomer-
ization of the substrate could be observed when CPA-4 was applied. BINAM-derived
phosphoric acids (BDPAs), such as CPA-5 and CPA-6, were found to be capable of
inhibiting the formation of the byproduct. This work represents the first example of
chiral counterion-controlled enantioselective Heck reactions and offers an alterna-
tive to those employing chiral ligands to control the stereochemistry. A comprehen-
sive density functional theory (DFT) study indicated that the critical step controlling
the enantioselectivity should be the migratory insertion of the Pd-aryl intermediate
bearing a chiral counter anion to the cyclic alkene [54]. A modified structure of the
intermediate Int-17′ was suggested based on the calculation results, in which the
chiral catalyst BDPA is dispositioned as a counterion bound to sodium bicarbonate,
rather than the palladium.
2.3 Conclusion
As highlighted in this chapter, the progress in the transition metal/PTC combined
catalysis, especially the asymmetric variants, has illustrated attractive characteristics
and potential of this concept. The incorporation of PTCs, either cationic or anionic,
into transition metal catalysis not only facilitates the transformations but also offers
a supplementary and reliable option for the stereocontrol. In addition, chiral Lewis
acid/onium bifunctional catalysts [55–60], chiral ammonium/phosphine hybrid lig-
ands [61–67], and the combination of PTC with metallic anions [68–72], which act
closely related to metal/PTC cooperative catalysis in terms of fundamental principle,
have emerged for the creation of the new transformations. Despite the remarkable
achievements made in the last two decades, when compared to other subfields of
metal/organo combined catalysis, the concept of asymmetric metal/PTC combined
catalysis, so far is still in its infancy stage. Formidable challenges, as well as oppor-
tunities on the other hand, remain in this area. First, metals in the binary system
for asymmetric catalysis are limited to palladium and iridium, and the combination
of PTC with other metals, such as rhodium and nickel, remains unexplored. Sec-
ond, the metal/PTC combined catalysis in the relay or sequential manner remains
undeveloped, although some effects have been made toward this field [73]. Finally,
besides simple cations and anions, PTCs are also known to transfer many other
R R R R
Pd2(dba)3 (5 mol%)
CPA-4 (10 mol%)
ArN2BF4 +
K2CO3, benzene/MTBE
10 °C Ar
26 40 41
Up to 94% ee
Base β-H
B* B*–H ≡ CPA-4
elimination
Pre-catalyst
R R
H
Pd(0) 40
ArN2 B* Oxidative ArPdLn B* B*
Insertion
addition Ar PdLn
Int-16 Int-17 Int-27
Ar
Ar O
O O N Ar Pd OH
O
P P O
OH H2O O N
O N OH Na *
P
Ar H2O O N
Ar
Ar = 2,4,6-(Cy) 3C6H2 CPA-5 , Ar = 4-Adamantyl-C6H4 Int-17′
CPA-4 CPA-6 , Ar = 1,4-Benzodioxane-C 6H4
Bn
MeO2C CO2Me O N O
41a O
82%, 85% ee
N N
Ph (with CPA-4)
O O
NTsBoc F3C
41b Ph
86%, 90% ee 41c 42
(with CPA-5) 70%, 86% ee 78%, 90% ee
Ph
(with CPA-5) (with CPA-6,
after hydrogenation)
Scheme 2.16 Pd/anionic PTC cooperatively catalyzed asymmetric Heck–Matsuda reaction

of cyclic alkenes and aryl diazonium salts. Sources: Avila et al. [53], Reddi et al. [54].
species such as acids [74], formaldehyde [75], radical anions [76], and ammonia [77].
These features actually offer additional dimensions for the development of asymmet-
ric transformations by virtue of metal and PTC cooperative catalysis.
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for Kaige, the policeman, insisted on roaming about the verandah
and kitchen, mainly occupied in consuming our tobacco. Had Debe
not been our servant, he would undoubtedly have been summoned
by his wife, and, this being his fifth offence in this direction, he would
have been sent a prisoner to Thursday Island. To show his penitence
he wore all day a black kerchief round his head; while, to smooth the
ruffled feelings of his wife, he bought from us (out of his next week’s
wages) some yards of red twill which he presented to her.”
Mr. Bruce has informed me by letter that early in 1899 Jimmy Rice
and Debe Wali had, for them, a serious quarrel. It happened in this
wise. Pedro, a Manila who had married Jimmy’s wife’s daughter by a
former husband, D. Pitt, had given Jimmy a small cutter. Jimmy’s
wife considered the boat was given to her as a present for her
daughter’s sake, so she began to “boss” the boat and crew. Debe
was captain, while Jimmy remained on shore to cook the bêche-de-
mer.
Jimmy’s troubles now began in earnest. First his wife thought that,
as she was owner of the boat, it was beneath her dignity to cook for
Jimmy, and told him when he asked for his breakfast or dinner to go
out and eat filth. Poor Jimmy asked Bruce for advice.
Shortly afterwards the “fish,” as bêche-de-mer is colloquially
termed, they obtained was demanded by Pedro, as owner of the
boat. This Jimmy gave him. Then the crew wanted their wages.
Jimmy said he had nothing to give them, that they were all his
friends, and had promised to work for nothing to clear the boat. Debe
Wali said no; he wanted wages. Jimmy and his wife had a bad time
of it, so the latter went to the Mamoose and summoned Jimmy for
wages.
The police then told Jimmy he was summoned; and great was the
clatter of tongues and mutual abuse. Debe ran into his house and
brought out a big rowlock of a boat, and stabbed Jimmy in the chest
with it. Of course it did not do Jimmy the least harm, but he
commenced shouting “Police! police!” knowing well enough that the
police were standing by and witnessing the whole affair. Of course
the police had to arrest Debe. Next day there was a cross-summons
in the court—one for wages, the other for assault.
We have here an interesting example of the confusion that arises
in the transition between one economic condition and another.
Formerly communal labour was the rule. If a well had to be sunk or a
house built, all friends would lend a hand, a feast with the
concomitant excitement being a sufficient immediate reward, the
reciprocity being, of course, fully recognised. Pedro’s loan of a boat
on the hire system of purchase is well understood. Before the white
man came it was customary for the Torres Straits Islanders to
purchase their canoes on what was virtually the three years hire
system. The crew demanding wages belongs to the new economic
custom introduced by the Europeans.
Pedro, the owner of the boat, was drowned in the hurricane that
swept across Northern Australia in March, 1899, and Jimmy had to
pay D. Pitt the balance due on the boat.
The new Erub (Darnley Island) church was to be opened in
September; and when the Murray Island contingent was about to
start to take part in the festivities, Finau could not get a passage for
himself or family unless he went with the Murray Islanders; so he
asked Jimmy to lend him his boat. Jimmy said he could not lend it.
Two months afterwards Jimmy’s cutter went to Garboi sandbank to
fish, and the crew slept on shore the first night. When they awoke
next morning no cutter was to be seen; she had parted her chain in
the night and had drifted away. So poor Jimmy lost his boat and all
his labour, and the worst of it is, he has the haunting fear that it was
the direct act of God because he did not lend his boat to the South
Sea teacher when he asked for it. All the people assert this is the
true explanation of his loss.
Jimmy is a happier man since his wife has ceased to be a
boatowner, as she now condescends to roast yams and cook fish for
him. Debe and he are as good friends as ever, and are always
plotting how they can get as many shillings as they can for the least
amount of work, and on the whole they succeed very well.
Debe is now the proud father of a pretty little daughter, and
devotes a good deal of his time to nursing it. Occasionally he has a
row with Kaima, his wife, when he considers she is not doing the
nursing in a scientific manner. Then he generally takes the
management of the baby for a time, but the infant does not fail to
proclaim when it is Debe’s watch on deck.
On Friday, August 4th, 1899, there were two earth tremors on
Murray Island. I cannot do better than transcribe Mr. Bruce’s vivid
description of the occurrence. “I had just sat down to lunch when the
iron roof and the verandah floor made such a clatter that I could not
at all make out what was wrong; about five minutes later there came
another and stronger shock. I jumped up and went on the verandah.
“There was a great crowd of men playing hockey on the sand
beach in front of the house, and at first I thought some of them had
been larking on the verandah, but when I went out everything was
quiet. They were sitting down; not a word broke the deathlike
stillness. I thought at first they were resting after their game, but
even then they never sit still. I asked, ‘What’s wrong’? Then some of
them came up and said, ‘Why, ground he jump up and down all the
same as sea’!
“Then it struck me at once what had happened. I asked them how
they felt when the shock came. They said the whole beach was
heaving like the sea so that they could not stand. Some said they felt
sick and wanted to vomit; others said everything looked blurred and
indistinct, and men’s faces were all distorted when they looked at
them.
“I was sorry I was in the house at the time, as I should have liked
to experience the sensation. I should think each shock must have
lasted about two minutes, with an interval of five minutes between
them.
“After evening school I saw some of those who had been to their
gardens on the top of the hill. From their description the earthquake
was felt worse up there. Pasi told me he was sitting down on the
ground nursing the baby when the first shock came, and he and the
baby commenced to bob up and down, and he felt as if he were
sitting on something that was giving way with him. When the second
shock came, the coconuts on the trees were bobbing up and down,
everything was trembling and swaying; a bucket on the ground
opposite him was jumping up and down. He thought it was the devil,
and that he was bewitched, so he got up and called his wife to come
away. Soon they met other frightened people running home. Pasi
said he was ‘very glad to hear all man feel him all the same as
myself.’
“No doubt the people received a great scare. They were going
about in quite a subdued manner for a few days. When Sunday
came they were told by Finau that God was angry with them. God
has been very angry with them here this year; they were told the
same after the hurricane took place. But then I remember the
Princess Alice disaster on the Thames was referred to in the same
manner by Mr. Spurgeon at the Tabernacle; so we cannot wonder at
the coloured teacher attributing all disasters to the wrath of an
offended Deity.
“I had rather an amusing reason given to me why the cyclone of
the 4th and 5th of March (1899) happened. There was a crowd of
boats anchored in the bay, and a South Sea man wanted to hold a
service on the beach, but very few went to hear him pray. Whilst he
was praying, some unregenerate nigger had the impiety to play on
his concertina. That day the hurricane came. The men who told me
this thoroughly believed, since the praying South Sea man had
asserted it, that God had sent the hurricane because of that man
playing the concertina.
“That is the kind of God they like to have described to them, and
no other. Really the South Sea teachers know the kind of God to
depict to the native far better than the white missionary does; his
God of Love is beyond their comprehension. They look as if they
believed in Him, but converse with them, and you find the God of
Wrath is their ideal of what God is. He takes the place of Bomai, etc.,
which they have lost.
“At the opening of the new church at Erub, in September, all the
South Sea teachers from the Torres Straits were gathered together.
Captain H⸺ had just come across an article in a newspaper,
written by some German scientist, that a comet was to appear in the
heavens some time in October, and that it would strike our planet on
the 5th of November. The Captain described the comet to the Erub
Mamoose, who in his turn told the assembled teachers, and they, not
unnaturally, went to Captain H⸺ for further information. The
Captain, nothing loth, gave them what they wanted, with a practical
illustration of how the comet would act when it came in collision with
the earth. He got a ball of paper and a stick, making the latter
violently strike the ball of paper, which flew some distance away.
‘That,’ said he, ‘is the way our world will go, and I know that Old Nick
is preparing his fires for a lot of you fellows now.’
“The teachers held a meeting, and arranged that when each
teacher went home to his station he was to appoint three weeks of
special prayer, and to beseech God not to allow the comet to destroy
the earth. Finau arrived here full of it, and the people with him arrived
equally full of influenza through living in over-crowded houses in
Darnley.
“On Sunday I went as usual to church. At the close of the service
Finau told all the people to remain, as a special service was to be
held; so I remained along with the rest.
“After a short interval Finau told them about the comet, and that a
very wise man had written in the newspaper that the world was
shortly to come to an end. This was true. He then read from the
Gospel of Mark, chapter xiii., from which he proved that this was the
time all these things were to happen, because this wise man said so
in the newspaper.
“He kept on until he had all the people in a proper state of fear.
Then he directly referred to me that I knew it was all true, and would
happen. I said ‘No.’ He took no notice, but told them that in three
weeks’ time, on the 5th of November, if God did not hear their
prayers, they would all be destroyed.
“After praying he invited anyone to stand up and pray and speak
on the subject of the comet. Immediately all the Murray Herschels
and Sir Robert Balls were on their feet, one after another,
expounding on comets and their destructive powers, and they also
finished up by saying, ‘Oh, it’s true! That wise man said so in the
newspaper.’ The subject suited them immensely.
“After they had all had their say, which occupied nearly two hours,
Finau told them from that day until the 5th of November there were
to be special prayers, asking God to rebuke the comet and make it
go another road away from the earth. They would all know in three
weeks’ time whether God had heard their prayers. If He did not
destroy the world then, that would be a sign that He had heard them,
and was pleased with them; but if the comet destroyed the earth on
the 5th of November, then they would understand that God was
angry with them, and wished to destroy them as a punishment.
“He then again referred to me as knowing it to be true. I had to get
up and speak (it was the first time I ever did so on church matters). I
told the people that I had not heard anything about this comet, and
that they were not to be afraid; that even if there was a comet, it was
not likely to interfere with our world, and even if it did, I thought no
harm would arise from it. They would all find, on the 5th of
November, Murray Island would be quite safe, and everyone would
be going about their work as usual. I might as well have said nothing;
but there was so much sickness about (mainly influenza) that I
thought this frightening of the people would have an injurious effect
on them.
“The 5th of November came round, and nothing extraordinary
happened. So Finau appointed the 6th to be a day of thanksgiving to
God, because He had heard and answered their prayers by turning
the comet away from the earth.
“Thanksgiving took the form of prayers in the morning, feasting
and games in the afternoon. So you may be sure I had a good time
of it in school that Monday afternoon with the noise of the
thanksgiving outside and the inattention of the children inside.
“You people in England ought to be truly thankful that we have
such effectual fervent prayers in this part of the world. I think this
answer to prayer is quite as good as any I read in Mr. Stead’s
Review of Reviews last year. All that was wanting to make the wise
man in the newspapers and Finau’s predictions perfect was to have
had the earth tremors introduced in November instead of August,
and then what a tableau!
“Captain H⸺ is delighted at the good work he considers he has
done in stirring up the people to such a time of prayer. In his last
letter he says he has been the means of leading these South Sea
teachers and the natives to more earnest prayer through fear than
has ever been done by any individual in the Straits before.
“The Mamoose and Pasi left for Erub to attend the memorable
opening of the church a fortnight earlier than the general public, but
before starting the Mamoose left strict orders with the sergeant if
anyone made a storm of wind while he was away to find him out and
have him punished. No sooner did he start than it blew ‘old boots’;
no boat could leave the island, and the Mamoose had a terrible
passage.
“Kadud, the new Sergeant of Police, came to me and told me he
was looking out for the person who had made the wind, as the
Mamoose had given him strict orders to have him punished by a fine.
One day he came, saying he had found a dry coconut leaf stuck in
the creek at Kiam, and thought he would find the party. Another day
he would find a similar leaf and a shell stuck in the sand on the
beach. Kadud was getting furious, and all the time it was blowing a
hurricane. The storm lasted four weeks, so that the majority of the
people from Murray Island were late for the opening ceremony.
“For months they tried to find out the miscreant; Wali, being a
church member now, is past suspicion. It would make you laugh to
hear how seriously the Mamoose and Kadud talk when I ask them if
they have found out who it was that made the ‘big wind.’ ‘Oh no,’
they reply; ‘by-and-by we shall catch him.’
“Mappa, a Murray Islander—one of the L.M.S. teachers—is here
at present on a six months’ leave of absence; he is a shrewd, sharp
fellow, but a thorough native. He brought with him a young fellow
named Wai from his station at New Guinea, another sharper, who
has already a great reputation on Murray Island of being able to
make, injure, and kill, and Mappa backs him up. Tuk is the form of
sorcery he is supposed to practise, and the Murray people are
terribly frightened of it; they tell me the New Guinea men are very
powerful in tuk, and from Kiwai they can kill a whole village full of
people on Murray Island, nearly a hundred miles away.
“Wai first began practising on William, the deacon, who lives at
Dio. He went with some others to Dio, and showed William two sticks
of tobacco, and said ‘Tuk.’ William began to shake when Wai told
him to go and look in his box and see if he had lost any tobacco.
William, still trembling, got his key, looked in the box, and said, ‘Yes.’
Wai held up the tobacco, and said, ‘This is it.’ William replied, ‘Yes,
that’s it.’ Wai exclaimed ‘Tuk,’ and the two sticks of tobacco
disappeared, much to the astonishment of the crowd. William
pressed a present on Wai, to secure himself against tuk. When
William told me about the affair I nearly exploded, trying to keep
serious, and endeavouring to sympathise with him. Wai is a smiling,
comedian-faced young fellow; he comes along to see me every other
day, and to have a smoke. Ulai and Mappa, a good pair, are always
extolling Wai’s great powers.
“A fortnight ago Mappa, who is taking Finau’s place, the latter
having gone on a visit to Mabuiag, had a crowd round him after a
Friday morning’s service, and used some strong language about
some men who had not attended church and about Kadud, who
owns a well at Kiam, about which he and the South Sea teacher
have a dispute.
“A woman named Deau went and told these men that Mappa was
speaking ill of them. They hurried along to the church compound,
Deau along with them. She then asked Mappa to repeat what he had
said, and told him he was bad man, that he thumped the pulpit with
his hand when preaching to them, and then went home and thumped
his wife. Mappa then began to tell her she was a bad woman, a
Samaria kosker—that is, a woman of Samaria. Deau could not stand
that, so she went to the police and summoned Mappa for swearing
at her by calling her a Samaria kosker. Mappa then threatened the
whole of Deau’s friends that he and Wai would put tuk on them all.
They were in a great panic; the sergeant, Kadud, was nearly white
when he came to see me, with some of the threatened people, and
asked if they could not arrest Mappa. They all declared that Mappa
had learnt tuk in New Guinea, and could destroy them all if he chose.
“Mappa was summoned for slandering Deau, and dismissed on
this count; next he was charged with threatening the people. The
witnesses all held that when Mappa went back to New Guinea he
would destroy anyone he chose by using the sorcery of tuk. It was
tuk, tuk, and nothing but tuk. I asked Mappa if he had threatened the
people with this, and he said he had, and that he was angry. I asked
him if, when he went back to New Guinea, he or the Fly River men
could shoot tuk to Murray Island. He said they could, but he was not
sure about himself. I warned him to think about what he was saying,
and if he really believed that Wai could do such a thing. He hummed
and hawed, and said ‘No.’ That was all I wanted in order to quiet the
fears of the people, so I asked Mappa to tell the Mamoose and the
people that the Fly River men could not injure them, and that neither
he nor Wai knew tuk. He told them so, but at the same time they did
not believe him, and would rather have heard him say that he and
Wai were au kali tuk le (very big tuk people). Mappa was dismissed
from court, and advised not to practise tuk any more whilst on his
holidays. The whole tuk affair has been very amusing. Mappa and
his wife are now teaching the Murray youths New Guinea dances, so
that they may beat the Dauar men on New Year’s Day.”
In a letter dated September 30th, 1900, Mr. Bruce gave us the
later history of some of our friends, and as it illustrates the social life
of the Murray Islanders in a very interesting manner, I do not hesitate
to print the greater part of it for the benefit of my readers.
“This year we are experiencing the results of a big drought. The
north-west monsoon, which generally brings a young deluge with it,
has been very mild this year, so mild, in fact, that but for the change
of winds we might say we had no ‘nor’-west.’ In December of 1899
we had good rains, which gave promise of a good harvest from the
gardens this year; but there has been such a dearth of rain in 1900
that all the garden stuffs died off. First the sweet potatoes went (that
is, the vines), for they never got to the length of tubers; then the
yams died off, but the people managed to get a few small ones out
of the crop. So the people are reduced to coconuts and bananas,
which are fairly plentiful. The natives are perfectly happy, carrying on
play night after night, and their boats lying idle at anchor, instead of
being at work getting black-lip shell, which has been a splendid price
this year, to buy flour and rice for their families. Douglas Pitt’s son
did very well with one boat working from here; he cleared £350 in six
months with a crew of mainland boys, whilst the Murray men did not
clear as many shillings with seven boats which they obtained from
individuals to work out and on shares. They kept on getting
advances (‘draws’) of calico and tobacco, and do no work.
“Your two ‘curry and rice chefs,’ Debe Wali and Jimmy Rice, both
got boats. Debe obtained all the draws he could out of the owner in
eight months, and collected about £4 worth of shell to pay about £10
worth of draws. The consequence was, when he went to Thursday
Island for more draws the owner took possession of his boat, and he
was lucky to get it, because if she had remained much longer at
Murray Island she would have broken up on the beach. Jimmy Rice,
poor fellow, has not been quite so fortunate as his friend Debe. In the
first place, he could not get so many draws out of his man as did
Debe, and he had signed before the Shipping Master, with a solicitor
to see that all was fair and square. When Jimmy got all the draws he
could from the owner of the boat, he and his crew refused to do any
work, and they were taken before the Shipping Master at Thursday
Island. The Shipping Master prosecuted them in court. All the crew,
beside Jimmy Rice and Toik, decided to go to work and finish the
time they had signed for. Jimmy and Toik held out, thinking they
would be sent back to Murray Island by the steamer, as she was
coming out the day following; but they made a mistake, and each of
them got two months in jail to work out their time. One of the young
Pitts paid for a boat here in four months with a mainland crew, and
although the Murray men have these object lessons before them,
they seem to be no incentives to make them go and do likewise,
which they could easily do.
“Papi has a boat on half-shares from a Manila man named Zareal,
a jeweller at Thursday Island. Like the others, Papi was doing no
work after getting what he could out of Zareal; but he was lucky
enough to find a good pearl in a shell, so he took it to Thursday
Island and sold it for £150, then went flashing about town. Zareal
came to know of the pearl, and claimed half of its value for the boat;
but Papi objected, and got away from Thursday Island to Murray
Island with the cash. Not a bad haul for a Murray man! There is likely
to be trouble about it, but I bet my boots Papi comes off the winner.
“You remember old Gasu; his eyes were bad. He is now quite
blind; can only tell the difference between night and day. He looks
physically well, but takes no exercise whatever, as he tells me he is
ashamed to go walking about with a boy to lead him. When I visit
him I give him a spin along the road, and he enjoys it immensely.
Poor old Gasu! He had not his equal on the island; a thorough,
genuine old gentleman, and quite free from all cant, although he had
his fears of the ‘White Man’s Zogo’ (the Church) like all the rest.
“The great drought this year has been put down to many causes.
Your party came in for some of the blame for taking away the good
doioms, so that the rain-makers were handicapped in giving a
plentiful supply. But the principal cause for a time was our old friend
Debe Wali; he was charged with defiling and throwing down the yam
zogo at Dauar, named Zegnaipur—this is the principal yam zogo.
Debe’s brother, Komabre, and Harry, the Murray Mamoose, were the
two head zogo men who prepare it every year. Komabre died last
year, and Debe, of course, believes someone was the cause of his
death, and the people say that he was angry at the death of
Komabre and knocked down the zogo, hence the drought. Mamoose
and Pasi came to me to have a talk about it, and wished to know if
they could not prosecute Debe in court. I told them they would have
to get proof that he had done the injury, well knowing they could get
none. Mamoose said he was certain Debe did the thing to spoil the
yams and food, and that the law should punish him. I had to cool him
off as best I could. The next one accused was Joe Brown. They said,
because he has a quarrel with Jimmy Dei, he burnt the coconut zogo
at Zeub by wilfully setting fire to the grass, and that he had stopped
rain from coming and blighted all the crops. It was very amusing
when I asked Debe and Joe confidentially why they had been and
gone and done it. A knowing smile stole all over their faces, as much
as to say, ‘I’ll teach them to interfere with me!’ Still, they would never
confess to anything, but you could see how pleased they were at the
prominent place they held among the people. When I represented to
them how they were making me suffer too from having empty water-
tanks, old Joe said, ‘By-and-by, Jack, you stop; I make him all right;
you see your tank full up by-and-by!’ That ‘by-and-by’ means so
much to them, and is such a handy phrase I don’t know what they
would do without it now!
“In the early part of the year I was pestered by the men who had
boats, and also by their crews, coming every day inquiring when the
big blow was to be. I told them it was impossible for me to fix any
stated time, but they knew we always had strong winds in the north-
west. It was of no use, they kept on coming to inquire. At last I asked
if anyone had been telling them there was to be a big blow. They
said yes, one man told them; but who he was they would not say. Of
course it made a good excuse for not going to work, and they made
the most of it and let the boats lie up.
“The following is an example of the power zogo men are credited
with. After Debe’s and Joe’s reputation was on the wane and being
forgotten, Mamoose and Jimmy Dei were in my house one day, and
the conversation turned on the everlasting drought, which both were
bewailing. I began to twit them about the powers of the rain-makers,
trying to bring them out. Mamoose did not like it, and began to
converse with his optics to Jimmy (Murray men do a lot of talk on the
quiet with their eyes). Jimmy assented, so Mamoose got up out of
his seat, looked out of the front door, then out of the back—to make
sure there was no one about who would be likely to hear—sat down
again, and after sundry ahems Mamoose whispered to me the real
cause of the drought. He said the rain-makers were afraid to make
rain and prepare the ceremony, in case they might make too much
wind along with it, and therefore cause another big hurricane, like
that of last March, and they feared the Government would punish
them if many lives were lost; besides, Gasu being now blind, he
could not see to prepare the zogo properly, and they were afraid to
make it! I had to condole with them on the hard luck of having to risk
the chances of either a cyclone or a famine, and agreed with them
that a famine was the safest, for, as Mamoose said, the hurricane
might smash up the island altogether. But I assured him at the same
time that the Government would on no account hold them
responsible for any damage done by any cyclone in this part of the
world. I never heard of any Murray man getting the credit of making
the hurricane last year; no doubt they have been afraid to hint at it,
and I have no doubt the people give the honour to some of the zogo
le for having caused that disaster.
“I had a gentleman living with me for a month or so; he came from
New Zealand, and is travelling all round, doing the ‘grand tour of
Australia, New Guinea,’ etc. He was grand company, although a very
strict churchman and an extreme ritualist. I had no idea colonial high
churchmen could be so high! He out-ritualed everything I had ever
seen or heard of, but he was one of the good sort who could give
and take a joke.
“We had a trip to Dauar one Saturday; went in the whale-boat, and
several passengers accompanied us. We had a walk all round, and
had a nice day of it. After we had returned home and had had
supper, and were sitting talking and smoking, a deputation headed
by Pasi, who is Mamoose of Dauar, came to inform me that those
who had accompanied us to Dauar had gone on purpose to see the
zogo of Wiwar. This is a round stone (sandstone) about the size of a
pumpkin; if it is prepared by a zogo man it has the power of causing
constipation, and the person affected will die if there is no antidote
used in the form of taking off the power of this zogo. Pasi had a
small packet in his hand, wrapped up very carefully, like tobacco, in
a dried banana leaf. He asked me if I would examine it, and spread it
out, telling me this was the cause of the sickness of an old lady
named Sibra. She remembered that the last time she had been over
to Dauar she had passed the zogo Wiwar, and now knew the cause
of her sickness. Her friends had gone over with us to find out if the
zogo was prepared; they were to take away the power of the zogo by
cleansing it with sea-water, and placing the leaf of a plant called gebi
on top of the stone, and pouring water over the stone. Pasi wished to
know if the police could apprehend old Lui, as he was the only Dauar
man who knew how to prepare the zogo. I asked Pasi how the zogo
was prepared; he said, ‘The zogole, after having a stool, placed the
excreta on the stone, using an incantation, in which he referred to
the person he wishes to blight.’ To prove the case, the friends went
to the stone and found it had been prepared, and brought away a
sample of the excreta with them. My visitor could not refrain from
laughing, although I warned him to keep serious. Pasi said there was
no chance of Sibra’s recovery, as the zogo had been prepared too
long. I was giving the old lady medicine, and thought she was going
on nicely, but on the Monday afternoon she died. Of course old Lui
got the credit of removing her, because they had had a quarrel of
words. The friends of Sibra do not consider our law of much account,
as Lui cannot be punished, even after the strong evidence they
brought to me. When Lui dies, his relatives will charge Sibra’s
relations with using a zogo, appropriate to whatever sickness he may
have been afflicted with.
“It was too much when Pasi asked my visitor to have a sniff, and
tell him if it was the real thing or not. He fairly exploded and roared,
and spoiled the whole effect, as I had to follow suit. The deputation
did not remain much longer, but carefully rolled up their sacred
bundle and left. They are very sensitive to ridicule, and do not like
their customs laughed at. The consequence was that they would not
for some time tell me anything that occurred of a similar nature. You
will perhaps think I ought to rebuke them and advise them not to
follow these old customs, but it is of no use doing this, as these are
so engrained into their everyday existence that they could not, as
yet, live without them. Their disappearance is, I think, only a matter
of time.
“It is very seldom that houses are burned down on Murray Island,
considering the inflammable material they are constructed of, and
the carelessness of the people with fire. This year, however, three
houses were burned down. The first one belonged to a widow
named Nicky. The people were all at one of their night plays, and
Nicky’s house was burned, and nothing saved. The play was a long
way from Nicky’s place, but it is considered that the spirit of her
deceased husband (Arus) was angry with her for her conduct, and
burned her house down. It was a serious loss to Nicky, as she has a
large family. I spoke to the Mamooses about getting the people to
assist her, and another widow, Anai, whose goods were also all lost
in the fire. The poor women had really saved nothing except their
petticoats. I gave them a start in goods, and I was really astonished
at the manner in which the people assisted; some gave her a
camphor-wood box, others half-bolts of calico, plates, spoons,
knives, and so forth, so the camphor-wood boxes were well filled
with useful articles, and calico galore. All vied in beating each other
in the giving line, and of course a ceremony was made in presenting
the goods. I only hope the next unfortunate will come off as well, but
I fear not, as it is so foreign to the Murray Islanders to give without
getting an equivalent in exchange. However, they deserve all credit
for the way in which they assisted Nicky and Anai, and ought to
make Arus’s lamar (spirit) leave the widow’s house alone in future.
The other houses were burned down in the daytime, and all the
contents saved.
“This year (1900) has been a fairly healthy year. Up to the present
there have been five deaths—two adults and three children. Matey is
dead; he was a young man about thirty years old; he died of
consumption, I think, and was ill for a long time. I tried to get him to
go to the hospital at Thursday Island, but he would not go. There is a
Queensland Aboriginal working in the boats at Darnley, who has
quite a reputation as a medicine-man. When Matey was very weak
he wished to be taken to Darnley to see this mainland boy. He was
taken over in a dying state. The mainlander had a look at him and
told him, ‘You fellow, you die; no more blood stop along you; two day,
three day, you finish!’ This consultation was quite satisfactory to
Matey and his friends, so Matey requested them to take him back to
Murray Island to die there. They started back with him, and as soon
as the anchor was dropped at Murray, poor Matey’s spirit took flight
to Boigu (an island to the west of Murray, where spirits are supposed
to live in a very happy state without any fears of brimstone).
“Murray Islanders have a great dread of dying anywhere than on
Murray, and no people have a greater love of their native land than
they have. Since this mainland boy on Darnley gave so good a
prognosis in Matey’s case, his reputation has gone up like a rocket,
and has not yet come down, several have gone over to consult him.”
The natives of Erub and the Murray Islands frequently used to
make mummies of their dead relations. The details of the process
are not particularly edifying, and need not be narrated here. The
wizened corpse, which might almost have been made of papier-
mâché, so light was it, was lashed to a bamboo framework. To be
made more presentable it was painted red and pieces of mother-of-
pearl from a nautilus shell were inserted in the orbits, a round spot of
black beeswax serving for a pupil. Finally the mummy was decked
with various ornaments. When it was complete and inodorous a final
feast would be provided, and it would be suspended in the house.
There the mummy would remain, swinging with every breath of wind
and turning its gleaming eyes with each movement of the head, until
it fell to pieces with old age.
When the body crumbled away word was sent to the friends to
come and assist in cutting off the head. A big feast was held, and a
man who was skilled in making portrait faces in beeswax on skulls
was also present. Later the artist made the wax model of the
deceased’s face; anyhow, the length of the nose was accurate, as
immediately after death the length of the nose was measured with a
piece of wood, which was safely kept for the purpose of securing the
right proportion of the imitation nose.
When the face was finished the head was given to the nearest
male relative. The men then cried. Later it was taken to the women,
who also had a good cry. The inevitable feast followed, at which the
artist received a large share of food.
The modelled and decorated skulls of relatives were kept probably
partly for sentimental reasons, as the people are of an affectionate
disposition, and like to have memorials of deceased friends, but
mainly for divinatory purposes.
A duly decorated skull when properly employed became a divining
zogo of remarkable powers, and was mainly used in discovering a
thief, or the stolen article, or a man who had by means of sorcery
made someone sick. But this could only be done by bezam le, or
members of the shark clan, who were also members of the Malu
fraternity. All who engaged in this hunt went in the early evening to
the zogo house, and one of the zogole took the Main mask and put it
on, repeating a certain formula. After leaving the house, the zogole
carried the skull in front of him, and all marched with a particular gait
till they heard a kind of grasshopper called kitoto, and they rushed in
the direction from which the noise proceeded. One particular kitoto
was believed to guide the men to the house of the offender. Should
the men lose the right direction the kitoto would wait for them to
come up, ever and again making its sound, “Sh, sh.” Ultimately they
were led to a house, and this must, of course, according to their
ideas, be the house of the malefactor.
It was of no use for the man to deny the evil deed, for kitoto had
found him out; and, moreover, the bezam le were so powerful that it
was as much as his life was worth to resist. If he happened to be a
bezam le himself he might try to brazen it out among his friends; but
if he was an outsider it would be useless, and he would have to pay
the fine.
I was naturally anxious to obtain one of these divining heads; even
by the time of my former visit they had all been done away with, at
least, so I was informed. I had therefore to be content to have a
model made for me. (Plate XII., B, No. 2; p. 139.)
First a skull had to be procured—and for other reasons I was very
desirous of making a collection of skulls; but it was long before I
could obtain any (I am referring now to my former visit), though I
constantly said, “Me fellow friend belong you fellow. ’Spose you get
me head belong dead man, I no speak. ’Spose you get him, I no
savvy what name you catch him, that business belong you fellow.
What for I get you fellow trouble?”
Eventually I came across a man who volunteered to get me some,
and I promised to give him sixpence per head; or, as I put it to him,
“One head belong dead man he sixpence, one head belong dead
man he sixpence; you savvy?” and as I spoke I touched and turned
down, native fashion, the fingers of the left hand, beginning with the
little finger. He understood perfectly.
Next day he brought me a basket of skulls, and he could tell me
the names of some of them, too! As he handed out one skull and
mentioned a man’s name, I noticed that the nursemaid of the
missionary’s wife, who was standing by, looked rather queer; but as
it was none of my business, I took no notice. Later I found that the
skull in question belonged to the girl’s uncle! I do not believe she
objected to my having the skull, but that the other man should have
the sixpence—the money had gone out of the family. When paying
the man I ticked off each skull on the fingers of my left hand, and
paid for it; but I had not enough sixpences, and so gave him half a
crown for five skulls. At this he looked very askance, although I
assured him the payment was quite correct. Fortunately Bruce was
standing by, and said he would give him five sixpences for it at the
store. My friend Baton made me one or two divining heads from
these skulls in the “old-time fashion.”
Hearing one day, during my former stay at Murray, that a woman
had died, and being grieved at the particular circumstances
attending her death, I determined to pay my visit of condolence. After
dark I went to the village where she had lived, and found her laid on
the beach with her head to the sea, and clothed in her best dress
and wearing her new hat, all her fancy calico being laid on the body.
The husband was sitting at the head, and close by were several
men, women, and children laughing and chattering over their
evening meal. Then the brother came up and bent over the body,
wailing and sobbing.
Shortly afterwards a canoe was brought to convey the corpse to a
more populous village, so that they might have a good cry.
Then I saw one of the most impressive sights it has yet been my
lot to witness. It was a beautiful tropical moonlight night, the sand
beach being illuminated with soft whiteness by the moon, and
countless stars glittered overhead. On one side the strand was
bordered by the gently lapping waves of the calm ocean, and on the
other by a grove of coconut palms, their grey stems, arising from a
confused shadow of undergrowth, topped by sombre feathery
crowns, a peaceful adjunct to a scene of sorrow, and the antithesis
of the ghastly mockeries of the funeral plumes of the professional
upholstery, which have only lately been abolished in England. A
small crowd of some twenty or so of us were walking along the
beach with the noiseless footfall of bare feet, keeping abreast of the
canoe which, with its sad freight, was poled along by the husband at
one end, and the brother at the other. As I saw the black silhouette of
the canoe and its crew against the moonlit sky and sea, silently
gliding like a veritable shadow of death, and heard the stillness of the
air broken by the moaning of the bereaved ones, my mind wandered
back thousands of years, and called up ancient Egypt carrying its
dead in boats across the sacred Nile—there with pomp, ceremony,
and imagery, here with simplicity, poverty, and stern realism.
At length we came to the village, the inclosure of which was
covered with family groups, mothers with babies surrounded by their
families, and many a little one was laid asleep upon the sand, well
wrapped up to keep off the flies.
The corpse was carried to a clear space, and again the gay
trappings of life were spread over the dead. An old woman, I believe
the deceased’s mother, came to the head, and sitting down, bent
over the body and commenced wailing. Then on all sides the cry was
taken up mainly by the groups of women who by this time had taken
their places round the dead. As one dropped out, another would join
in, and so with varying accessions in volume, occasionally dying
away to all but silence, the mournful sound continued through the
night, rising and falling in weird manner, recalling to my memory the
keening I had heard in far-away Kerry eighteen months previously.
Then I left them. The dead one surrounded by a changing circle of
weeping women; beyond, the family groups each illumined by its
own flickering fire, babies asleep, children playing, adults talking,
young men laughing, and a little love-making taking place in the
background; and above all the quiet, steady, bright face of the moon
impassively gazing, like Fate, on the vicissitudes of human life.
CHAPTER VII
KIWAI AND MAWAITA
We left Murray Island at 10 a.m., September 8th, by the Nieue,

which the Rev. James Chalmers very kindly sent to us. A small
crowd assembled to bid us farewell, and I know many of the natives
were genuinely sorry that we were leaving. We spent such a happy
and profitable time there, that we shall always have a soft corner in
our hearts for this beautiful island.
We reached Erub (Darnley Island) about 3 p.m., landed, and
called on Captain H⸺, who entertained us with his reminiscences
of New Guinea. We sailed at daybreak next morning, and reached
Daru in the early afternoon. About midday we ran on to a sandbank,
but as the tide was rising this did not much matter; in fact, it was
rather convenient, as we were thus enabled to have a meal on a
steady boat, a matter of importance to some of our party.
At Daru we were boarded by Mr. H. W. de Lange, the Sub-
Collector of Customs. Our little formal business was soon over, and
we then called on the Hon. Bingham A. Hely, the very efficient
Resident Magistrate. He kindly asked us to dinner, and we had an
interesting talk about the natives of his division. Mr. Hely has lately
made some observations on the important subject of totemism. On
Sunday, September 11th, we arrived at Saguane in the forenoon,
and Tamate, my old friend the Rev. James Chalmers, who has been
described as the Livingstone of New Guinea, gave us a hearty
welcome.
Unfortunately Mrs. Chalmers was ill with fever, which had
prostrated her for some time. Tamate, as he likes to be called by his
black and white friends, had also been quite ill from the effects of a
nasty fall from a verandah in the dark, and he was scarcely well yet;
indeed, it appeared to me that his health was much shaken, and no

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Asymmetric Organo-Metal Catalysis:

Concepts, Principles, and Applications

Metal-Catalyzed Asymmetric Hydrogenation. Evolution and

Supply Chain Analytics: Concepts, Techniques and

Hierarchical architecture of two-dimensional Ti3C2

Process Industry Economics: Principles, Concepts and

Principles of Metal Refining and Recycling Engh

Chiral Building Blocks in Asymmetric Synthesis:

Advanced nanomaterials for catalysis and energy:

Metal Oxide-Based Nanofibers and Their Applications

Concepts, Principles, and Applications

Cover Design: Wiley Library of Congress Card No.: applied for

Bibliographic information published by

© 2022 WILEY-VCH GmbH, Boschstr. 12,

All rights reserved (including those of

Print ISBN: 978-3-527-34592-2

Typesetting Straive, Chennai, India

Printed on acid-free paper

1 Why Is Organo/Metal Combined Catalysis Necessary? 1

2 Metal/Phase-Transfer Catalyst Combined Catalysis 19

3 Enamine-Metal Combined Catalysis 39

3.4 Catalytic Asymmetric α-Alkenylation, α-Arylation, and

4 Iminium and Metal Combined Catalysis 75

5 Brønsted Acid and Transition Metal Cooperative Catalysis 91

6 Metal-Brønsted Acid Relay Catalysis 125

6.2.5 Relay Catalysis Involving the Addition of Carbon Nucleophiles to

7 Lewis Base–Lewis Acid Cooperative Catalysis 179

8 Lewis Base-Transition Metal Cooperative Catalysis 241

8.3 N-Heterocyclic Carbene and Transition Metal Cooperative

9 Chiral Organocatalyst Combined with Transition Metal Based

10 Applications in Organic Synthesis 301

Why Is Organo/Metal Combined Catalysis Necessary?

(b) Oxidative addition Reductive elimination

Figure 1.1 Transition metal-catalyzed reactions initiated with oxidative addition.

Figure 1.2 Representatives of high-valent metal catalysis.

complete dependence upon the interactions between a highly active functionality

1.2 Early Stage of Organo/Metal Combined Catalysis

The combination of asymmetric organocatalysis and metal catalysis integrates the

Concepts of OC Active intermediates Applicable substrates Reaction types

Enamine catalysis Enolizable aldehydes and Aldol reaction

Iminium catalysis Enal and enones Michael addition

Brønsted acid catalysis H H Aldehydes, ketones, and Reduction

NHC catalysis Aldehydes Annulation

Enals, enones, and [3+2] cycloaddition

O N [Pd(allyl)Cl]2 MeO N [Pd(allyl)Cl]2

Figure 1.3 Pd and PTC cooperative catalysis.

Figure 1.4 Pd and phosphine cooperative catalysis.

opens up a window to seek unconventional modes to address issues of the stereo-

Figure 1.5 Lewis acid and Lewis base cooperative catalysis.

Cat. b and reactant D are added

Figure 1.7 Categories of asymmetric organocatalysis combined with metal catalysis.

1.3 Organo/Metal Cooperative Catalysis

Figure 1.8 Strategies of stereochemical control in cooperative catalysis. (a) Combine

(R)-38 39a 39b

Figure 1.12 Stereodivergent cooperative catalysis. Source: Modiﬁed from Krautwald

1.3.2 Cooperative Activation of Chemical Bonds

Figure 1.14 Asymmetric allylic C–H functionalization by cooperative catalysis.

Figure 1.15 Asymmetric organocatalysis combined with photocatalysis. Source: Modiﬁed