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SPRINGER BRIEFS IN MOLECULAR SCIENCE
GREEN CHEMISTRY FOR SUSTAINABILITY
Huanfeng Jiang
Chuanle Zhu
Wanqing Wu
Haloalkyne
Chemistry
123
SpringerBriefs in Molecular Science
Green Chemistry for Sustainability
Series editor
Sanjay K. Sharma, Jaipur, India
More information about this series at http://www.springer.com/series/10045
Huanfeng Jiang Chuanle Zhu
•
Wanqing Wu
Haloalkyne Chemistry
123
Huanfeng Jiang Wanqing Wu
School of Chemistry and Chemical School of Chemistry and Chemical
Engineering Engineering
South China University of Technology South China University of Technology
Guangzhou Guangzhou
China China
Chuanle Zhu
School of Chemistry and Chemical
Engineering
South China University of Technology
Guangzhou
China
ISSN 2191-5407 ISSN 2191-5415 (electronic)

SpringerBriefs in Molecular Science
ISSN 2212-9898
SpringerBriefs in Green Chemistry for Sustainability
ISBN 978-3-662-48999-4 ISBN 978-3-662-49001-3 (eBook)
DOI 10.1007/978-3-662-49001-3
Library of Congress Control Number: 2015955865
Springer Heidelberg New York Dordrecht London

© The Author(s) 2016
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this
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the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
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for any errors or omissions that may have been made.
Printed on acid-free paper
Springer-Verlag GmbH Berlin Heidelberg is part of Springer Science+Business Media

(www.springer.com)
Preface
Green method, atom economy, and concise synthesis are terms frequently
mentioned in chemistry-related publications and presentations nowadays. Inspired
by the requirements of green and sustainable chemistry, considerable efforts have
been devoted to developing general and practical methods to construct complex
molecules by taking advantages of chemical reagents with diverse and tunable
reactivity. Haloalkynes, such as bromoalkynes, chloroalkynes, and iodoalkynes, are
a significant class of molecules that have these futures and been widely utilized in
organic synthesis.
This book summarizes the general methods to prepare haloalkyne reagents and
also presents the selected examples to highlight the progress on the development
and applications of convenient and concise synthetic approaches involving
haloalkynes. According to the reactive sites of haloalkynes involved in the trans-
formations, we classify these reactions into three types: (i) the transformations of
carbon–halo bond motif; (ii) the diverse functionalization of carbon–carbon triple
bond unit; and (iii) the reactions involving both carbon–halo bond motif and car-
bon–carbon triple bond unit. The emphasis is put on the reaction mechanism
aspects and the synthetic utilities of the obtained products.
The primary purpose of this book is to illustrate the diverse reactivities and
applications of haloalkyne reagents, to describe the experimental techniques
of these valuable transformations in detail, as well as to enlighten the researchers to
answer the unsolved problems in haloalkyne chemistry. This book should be useful
to researchers in organic and organometallic chemistry as well as catalysis from
both academia and industry. Significantly, doctorate students and postdoctoral
researchers should be motivated by these innovations in chemistry.
v
vi Preface
I am especially grateful to the cooperative contributions made by all the authors.

Without their efforts and expertise, this book would not have been possible. I would
also like to thank the organizational support from Springer to overcome the troubles
encountered in the production of this book.
Guangzhou, China Huanfeng Jiang

September 2015
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Preparation of Haloalkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3 Reactions of Haloalkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1 Transformations of Carbon-Halo Bond Motif . . . . . . . . . . . . . . . 9
3.1.1 Construction of Carbon-Carbon Bond . . . . . . . . . . . . . . . 10
3.1.2 Construction of Carbon-Nitrogen Bond . . . . . . . . . . . . . . 33
3.1.3 Construction of Carbon-Sulfur Bond . . . . . . . . . . . . . . . . 35
3.1.4 Construction of Carbon-Phosphorus Bond . . . . . . . . . . . . 36
3.2 Transformations of Carbon-Carbon Triple Bond Motif . . . . . . . . . 37
3.2.1 Nucleophilic Additions. . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2.2 Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.3 Transformations Involved Both Carbon-Halo
Bond and Carbon-Carbon Triple Bond Motif . . . . . . . . . . . . . . . 57
3.3.1 Initially Reacted at the Carbon-Halo Bond . . . . . . . . . . . . 57
3.3.2 Initially Reacted at the Carbon-Carbon Triple Bond. . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
vii
Abbreviations
Ac Acetyl
Ad Adamantyl
BINAP 2,2′-Bis(diphenylphosphino)-1,1′-binaphtyl
Bn Benzyl
BQ Benzoquinone
Bu Butyl
COD Cyclooctadiene
Cp Cyclopentadienyl
Cy Cyclohexyl
DABCO 1,4-Diazabicyclo[2.2.2]octane
dba Dibenzylideneacetone
DCE 1,2-Dichloroethane
DCM Dichloromethane
DMAP 4-Dimethylaminopyridine
DMEDA N,N′-Dimethyl-1,2-ethanediamine
DMF Dimethylformamide
DMSO Dimethyl sulfoxide
Equiv Equivalent(s)
Et Ethyl
h Hour(s)
HMPT Hexamethyl phosphoryl triamide
ILs Ionic liquids
iPr Isopropyl
NBS N-Bromosuccinimide
NHC N-Heterocyclic carbene
NIS N-Iodosuccinimide
Nu Nucleophile
OTf Trifluoromethanesulfonic
PE Petroleum ether
Ph Phenyl
Py Pyridyl
ix
x Abbreviations
1,10-phen 1,10-Phenanthroline
rt Room temperature
scCO2 Supercritical carbon dioxide
Sia (Secondary)isoamyl
TBAB Tetrabutylammonium bromide
TBAF Tetrabutylammonium fluoride
TBHP tert-Butyl hydroperoxide
TBS tert-Butyldimethylsilyl
TEA Triethyl amine
TEMPO 2,2,6,6-Tetramethylpiperidine 1-oxyl
THF Tetrahydrofuran
TIPS Triisopropylsilyl
TLC Thin-layer chromatography
TMEDA Tetramethylethylenediamine
TMS Trimethylsilyl
Tol 4-Methylphenyl
Chapter 1
Introduction
Abstract Inspired by the demand of green and sustainable chemistry, modern

synthetic chemists have devoted to develop general and practical methods to
construct complex molecules. Due to the sp hybridization of the triple bond and the
connected halogen atom, haloalkynes, such as bromoalkynes, chloroalkynes and
iodoalkynes, have shown both controllable electrophilic and nucleophilic proper-
ties, rendering them highly versatile and robust synthons. As the immense use-
fulness of haloalkynes, impressive efforts have been devoted to this area in the past
decades and many novel chemical reactions have been developed. In this chapter,
we will introduce the physical property of haloalkynes, classify the reaction
intermediate types derived from haloalkynes, and also hope to give the readers a
comprehensive understanding of haloalkyne chemistry.

Keywords Green and sustainable chemistry General and practical methods

Haloalkyne chemistry Controllable electrophilic and nucleophilic properties
Versatile and robust synthons
The development of efficient and practical synthetic methods upon readily available
reagents to construct molecular complexity has greatly accelerated the advancement
of synthetic chemistry and related subjects. Inspired by the demand of green and
sustainable chemistry, modern synthetic chemists have devoted to develop general
and practical methods to construct complex molecules, as well as maximizing atom
economy and minimizing synthetic steps [1]. During the past few decades, con-
siderable progress has been achieved to fulfil these goals by taking advantages of
chemical reagents with diverse and tunable reactive properties. Among them,
haloalkynes, such as bromoalkynes, chloroalkynes and iodoalkynes, are a signifi-
cant class of molecules that have been widely utilized in organic synthesis [2].
Generally, haloalkynes, especially iodoalkynes, are good Lewis acids. In 1981,
Laurence and co-workers have demonstrated that the Lewis acidity of haloalkynes
could affect the vibrational spectra of these compounds [3]. In 2000, Goroff and
co-workers reported an unusual solvent effect, in which the solvent could signifi-
cantly change the 13C NMR chemical shift of iodoalkynes 1 and 2 (Table 1.1) [4].
© The Author(s) 2016 1

H. Jiang et al., Haloalkyne Chemistry, SpringerBriefs in Green Chemistry
for Sustainability, DOI 10.1007/978-3-662-49001-3_1
2 1 Introduction
13
Table 1.1 C NMR chemical shifts of 1 and 2 (in ppm)
Compound 1 in δ(A) δ(B) δ(C)

CDCl3 0.9 78.5 59.7
DMSO-d6 14.6 76.3 58.8
Compound 2 in δ(A) δ(B) δ(C, D)
CDCl3 1.9 78.8 58.8, 62.0
DMSO-d6 17.9 77.4 58.3, 62.7
Later, they confirmed that it was a general phenomenon. The chemical shift of C-1
in 1-iodo-2-phenylethyne (3) is 6.2 ppm in CDCl3, but moves to 17.7 ppm in
DMSO-d6 and 19.4 ppm in pyridine-d5 (Table 1.2) [5]. Computational evidences
indicated that this solvent effect came directly from polarization of iodoalkyne triple
bond in a Lewis acid-base complex with the solvent. It could predict that an
increase in the electron density at C-1 would lead to a decrease in chemical shift.
Due to the sp hybridization of the triple bond and the connected halogen atom,
haloalkynes show both controllable electrophilic and nucleophilic properties, ren-
dering them highly versatile and robust synthons. Traditionally, haloalkyne
reagents are served as a source of acetylides through metal-halogen exchange
(Scheme 1.1, A). Until 1943, Ott [6] disclosed that haloalkyne derivatives could
also be employed as equivalents of electrophilic acetylenic moiety, which would go
through an addition-elimination procedure upon the reaction with nucleophiles.
Importantly, the first enantioselective version was realized by Jørgensen [7] with
the treatment of a chiral phase-transfer catalyst in 2006 (Scheme 1.1, B).
Additionally, Boger [8] and Gevorgyan [9] reported respectively that haloalkynes
could serve as effective sources of the corresponding X+ ion or both X+ and
acetylide ions in the presence of organolithium species (Scheme 1.1, C and D).
Noteworthy, as the continuous efforts of Jiang’s group, the potential reactive
abilities of haloalkyne reagents became fully apparent along with the development
13
Table 1.2 C NMR chemical shifts of 3 formed Lewis acid-base complexes (in ppm)
Compound 3 in δ(A)
CDCl3 6.2
DMSO-d6 17.7
pyridine-d5 19.4
1 Introduction 3
of transition metal catalysis [2]. Generally, under the treatment of transition metal
catalysts, haloalkynes can be deemed as a dual functionalized molecule. Depending
on reaction conditions, several reaction intermediates, such as σ-acetylene-metal
complex (Scheme 1.1, Type I), π-acetylene complex (Scheme 1.1, Type II) and
halovinylidene-metal complex (Scheme 1.1, Type III) can be formed and undergo
further transformations to construct various of useful compounds. Additionally, the
reactive halogen substituents can be further functionalization, which permits the
rapid assembly of structural complexity. As the immense usefulness of haloalkynes,
impressive efforts have been devoted in this area in the past decades and many
novel chemical reactions have been developed [10].
In this book, we will classify the general methods to prepare haloalkyne reagents
and also present selected examples to highlight the progress on the development
and applications of convenient and concise synthetic approaches involving
haloalkyne reagents. The designed methods, as well as serendipitous observations
will be discussed with special emphasis on the mechanistic aspects and the syn-
thetic utilities of the obtained products, aiming to illustrate the potential applications
of haloalkyne chemistry in a wide spectrum of fields, including natural-product
synthesis, materials science, and bioorganic chemistry. Importantly, the general
procedure for each transformation of haloalkynes is described in detail. This book
should be useful to researchers in organic and organometallic chemistry as well as
catalysis both from academia and industry. Significantly, doctorate students, post-
doctoral researchers and young researchers should be motivated by these innova-
tions in chemistry. We hope this book could not only draw the blueprint of
haloalkyne chemistry, and help the readers to comprehensively know and under-
stand the diverse reactivities and applications of haloalkyne reagents, but also could
be used as a handbook for researchers to develop novel catalytic systems to answer
the unsolved challenges in haloalkyne chemistry and exploit new research areas.
Terminal Alkynes Aryl Halide

C(sp2)-X
Haloalkynes
Terminal Alkenes R X C(sp)-X Allyl Halide
R [M] X
A (M-X Exchange) Type I
R
Ott, Jørgensen
B R (Addition-Elimination) Type II
R X + [M] R X
C X Boger [M]
X = Cl, Br, I
D R and X Gevorgyan Type III X

C [M]
R
Scheme 1.1 Potential reaction pathways of haloalkynes in transition metal catalysis

4 1 Introduction
References
1. Li C, Trost BM (2008) Green chemistry for chemical synthesis. Proc Natl Acad Sci
105:13197–13202
2. Wu W, Jiang H (2014) Haloalkynes: a powerful and versatile building block in organic
synthesis. Acc Chem Res 47:2483–2504
3. Laurence C, Queignec-Cabanetos M, Dziembowska T, Queignec R, Wojtkowiak B (1981)
1-Iodoacetylenes. 1. Spectroscopic evidence of their complexes with Lewis bases.
A spectroscopic scale of soft basicity. J Am Chem Soc 103:2567–2573
4. Gao K, Goroff NS (2000) Two new iodine-capped carbon rods. J Am Chem Soc 122:
9320–9321
5. Rege PD, Malkina OL, Goroff NS (2001) The effect of Lewis bases on the 13C NMR of
Iodoalkynes. J Am Chem Soc 124:370–371
6. Ott E, Dittus G (1943) Polymerisation und Reaktionen mit Ammoniak, Aminen, Alkoholaten
und Natriummalonester. Chem Ber 76:80–84
7. Poulsen TB, Barnardi L, Aleman J, Overgaard J, Jørgensen KA (2007) Organocatalytic
asymmetric direct α-alkynylation of cyclic β-ketoesters. J Am Chem Soc 129:441–449
8. Boger DL, Brunette SR, Garbaccio RM, Boger DL, Brunette SR, Garbaccio RM (2001)
Synthesis and evaluation of a series of C3-substituted CBI analogues of CC-1065 and the
Duocarmycins. J Org Chem 66:5163–5173
9. Trofimov A, Chernyak N, Gevorgyan V (2008) Dual role of Alkynyl halides in one-step
synthesis of Alkynyl epoxides. J Am Chem Soc 130:13538–13539
10. Brand JP, Waser J (2012) Electrophilic alkynylation: the dark side of acetylene chemistry.
Chem Soc Rev 41:4165–4179
Chapter 2
Preparation of Haloalkynes
Abstract Traditionally, haloalkynes were accessible through the deprotonation of

the corresponding terminal alkynes with a strong base, followed by trapping with a
halogenating reagent. During the past decades, several mild and convenient
methods have been developed, thus increasing the attractiveness of this class of
compounds in organic synthesis. Among which, the electrophilic bromination of
terminal alkynes with N-bromosuccinimide (NBS) and Ag catalyst is one of the
most commonly used methods for the preparation of bromoalkynes due to the mild
reaction conditions, high efficiency and simple manipulation. In this chapter, we
will detailedly describle the general and practical methods to prepare bromoalkynes,
chloroalkynes, and iodoalkynes.
Keywords Terminal alkynes

Ag catalyst Bromoalkyne synthesis

Chloroalkyne synthesis Iodoalkyne synthesis
Haloalkynes were traditionally accessible through the deprotonation of the corre-

sponding terminal alkynes with a strong base, followed by trapping with a halo-
genating reagent. Recently, several mild and convenient methods have been
developed (Scheme 2.1), [1] thus increasing the attractiveness of this class of
compounds in organic synthesis. Among which, the electrophilic bromination of
terminal alkynes with N-bromosuccinimide (NBS) and Ag catalyst [2] is one of the
most commonly used methods for the preparation of bromoalkynes due to the mild
reaction conditions, high efficiency and simple manipulation (Scheme 2.2) [3].
General Procedure for the Synthesis of Bromoalkynes: To a solution of alkyne
(1 equiv) in acetone (0.2 mmol/mL) was added NBS (1.1 equiv) and AgNO3
(10 mol%) at room temperature with magnetic stirring. After 2–3 h, the reaction
mixture was diluted with hexanes (100 mL) and filtered off the crystals formed. The
filtrate was concentrated under reduced pressure and passed through a pad of silica
gel using hexanes as an eluent. The filtrate was collected and evaporated under
reduced pressure to afford a pure colorless oil of bromoalkyne.
General Procedure for the Synthesis of Chloroalkynes: To a solution of alkyne
(1 equiv) in CCl4 (2 mmol/mL) was added Cs2CO3 (1.1 equiv) and Bu4NCl (5 mol
%) at 70 °C with magnetic stirring. After 6–7 h, the reaction mixture was diluted

6 2 Preparation of Haloalkynes
R COOH R R
R n-C4H9Li 1) EtMgBr R TMS

NB NBS TBATFA NCS THF/HMPT 2) I2
S
IS
A
gN
3
O
gN
O3
A
CBr4/KOH I2, DMAP
R R Br R Cl R I R
CH2Cl2
M
AF I(P eO
Na
TB M
F y)
Br D 2 B
NBS CCl4 KI, TBHP F
4
R AgNO3 K2CO3 MeOH R
Br
R TMS R R
Scheme 2.1 Preparation methods for haloalkynes
Me
Br Me Br
Me Br
MeO Br F Br TIPS Br
Br
EtO2C Br Cl
I
Et Cl I
Scheme 2.2 Representative haloalkynes
with hexanes (100 mL) and filtered off the crystals formed. The filtrate was con-
centrated under reduced pressure and passed through a pad of silica gel using
hexanes as an eluent. The filtrate was collected and evaporated under reduced
pressure to afford a pure colorless oil of chloroalkyne.
General Procedure for the Synthesis of Iodoalkynes: To a solution of alkyne (1
equiv) in acetone (0.2 mmol/mL) was added NIS (1.1 equiv) and AgNO3 (10 mol
%) at room temperature with magnetic stirring. After 2–3 h, the reaction mixture
was diluted with hexanes (100 mL) and filtered off the crystals formed. The filtrate
was concentrated under reduced pressure and passed through a pad of silica gel
using hexanes as an eluent. The filtrate was collected and evaporated under reduced
pressure to afford a pure colorless oil of iodoalkyne.
References 7
References
1. For a review on preparation of haloalkynes, see: Zhdankin VV (1995) Alkynyl halides and
chalcogenides. In: Katritzky AR, Meth-Cohn O, Rees CW (eds) Comprehensive organic
functional group transformations. Pergamon, New York, pp 1011–1038
2. Nishikawa T, Shibuya S, Hosokawa S (1994) One pot synthesis of haloacetylenes from
trimethylsilylacetylenes. Synlett 7:485–486
3. Gao Y, Yin M, Wu W, Huang L, Jiang H (2013) Copper-catalyzed intermolecular oxidative
cyclization of haloalkynes: synthesis of 2-halo-substituted imidazo[1,2-a]pyridines, Imidazo
[1,2-a]pyrazines and Imidazo[1,2-a]pyrimidines. Adv Synth Catal 355:2263–2273
Chapter 3
Reactions of Haloalkynes
Abstract Haloalkynes are a significant class of molecules that have been widely
utilized in organic synthesis. In this chapter, we will describe representative
examples of haloalkynes, with particular attention paid to the reaction design and
mechanistic investigation as well as the general experimental procedures.
According to the reactive sites of haloalkynes involved in the transformations, the
reactions are classified to three types: (i) the transformations of carbon-halo bond
motif; (ii) the diverse functionalization of carbon-carbon triple bond unit; (iii) the
reactions involved both carbon-halo bond motif and carbon-carbon triple bond unit.
These transformations present a powerful tool for haloalkynes to construct
molecular complexity efficiently.
Keywords Haloakyne reagents

Diverse transformations Reactive sites

Reaction design Mechanism investigation
In this chapter, the emphasis will be put on the reaction development of haloalk-
ynes. According to the reactive sites of haloalkynes involved in the transformations,
the reactions are classified to three types: (i) the transformations of carbon-halo
bond motif (Scheme 3.1, path A); (ii) the diverse functionalization of carbon-carbon
triple bond unit (Scheme 3.1, path B); (iii) the reactions involved both carbon-halo
bond motif and carbon-carbon triple bond unit (Scheme 3.1, path C). These
transformations present a powerful tool to construct molecular complexity effi-
ciently. Representative examples are described, with particular attention paid to the
reaction design and mechanistic investigation.
3.1 Transformations of Carbon-Halo Bond Motif
Alkyne motif is one of the most important and useful building blocks in natural
products, pharmaceuticals, as well as functional materials. Subsequently, the con-
struction of alkyne motif contained molecules has attracted considerable attention
during the past decades. Transformations of haloalkyne reagents based on the

10 3 Reactions of Haloalkynes
R C X R C C X R C C X
Carbon-Halo Bond and

Reactive Sites: Carbon-Halo Bond Carbon-Carbon Triple Bond Carbon-Carbon Triple Bond
path A path B path C
Scheme 3.1 Reactive sites of haloalkynes
highly reactive carbon-halo bond, could realize the facile synthesis of skeletons that
previously were unable or difficult to prepare.
3.1.1 Construction of Carbon-Carbon Bond
3.1.1.1 Construction of C(sp)–C(sp) Bond
Conjugated diynes, especially 1,3-diyne compounds, are of vital significance as

versatile building blocks in the synthesis of natural products, bioactive compounds,
as well as functional materials [1, 2]. Consequently, the construction of conjugated
diynes has attracted great attention for a long time.
C(sp)–C(sp) Homo-Coupling
Due to the importance of symmetrical 1,3-diyne compounds, they are usually

synthesized either by Cu-catalyzed homo-coupling reactions including Glaser
coupling [3], Eglinton coupling [4], Hay coupling [5, 6], and Pd-mediated
homo-coupling reactions [7] or other related modified methods [8]. In this context,
the homo-coupling of haloalkynes would provide an alternative route to access
1,3-diyne compounds. In 2003, Lee’s group [9] documented a highly efficient Pd0-
catalyzed homo-coupling reaction of 1-iodoalkynes to construct symmetrical
1,3-diynes under mild and simple reaction conditions. This reaction did not use
copper salts or other metal reagents and a base, and was conducted under an inert
atmosphere, thus preventing side reactions associated with the Glaser coupling
reaction in which O2 is usually used as the oxidant. Although the exact mechanism
of this homo-coupling reaction of 1-iodoalkynes was not clear yet, the author
proposed that the formation of dialkynylpalladium intermediate (1) through the
oxidative addition product of Pd0 to 1-iodoalkyne reacted with another
1-iodoalkyne, which then converted to the 1,3-diyne and iodine (Scheme 3.2).
General Procedure for Pd-Catalyzed Homo-Coupling Reactions of Iodoalkynes:
To Pd(PPh3)4 (4 mol%) was added a solution of 1-iodoalkyne (1 mmol) in dry N,N-
dimethylformamide (DMF) (2 mL) under a nitrogen atmosphere. After 2–5 h, the
mixture was poured into an aqueous saturated NaHCO3 solution (15 mL) and then
extracted with diethyl ether (15 mL × 3). The combined organics were washed with
3.1 Transformations of Carbon-Halo Bond Motif 11
Pd(PPh3)4 (4 mol%)
R I R R
DMF, rt, 5 h
8 examples
R = alkyl, aryl 70-95% yields
R R Pd0 R I
PdII R 2
R PdII I
1
I2 R I
Scheme 3.2 Pd-catalyzed homo-coupling reactions of iodoalkynes
brine (15 mL), dried with anhydrous MgSO4, filtered, and concentrated under
reduced pressure. The residue was purified by silica gel column chromatography to
give the corresponding 1,3-diyne.
Given the environmental and economical factors, the development of transition
metal-free reaction systems for the construction of 1,3-diynes is highly demanded.
In 2010, Jiang’s group [10] successfully developed an efficient synthetic method to
1,3-diynes from haloalkynes under the treatment of KI in DMF solvent. This
approach also featured both oxidant and base free (Scheme 3.3). Generally, better
yields of symmetrical 1,3-diynes were obtained from iodoalkynes than the corre-
sponding bromoalkynes. Both aromatic and aliphatic alkynyl halides could perform
this homo-coupling reaction smoothly under the standard reaction conditions. And
diverse functional groups on haloalkyne substrates, such as fluoro, chloro, hydro-
xyl, nitrile group could be tolerated. To the reaction mechanism, the author pro-
posed the involvement of iodoalkyne intermediate generated from the substitution
of bromoalkyne with KI, which might undergo two pathways for the obtained
1,3-diyne product. The iodoalkyne would be transformed to iodine- and
alkyne-radicals, which were then homo-coupled to deliver the symmetrical
1,3-diyne and iodine (Scheme 3.3, path A). Alternatively, the iodoalkyne inter-
mediate was decomposed to iodine and alkyne anion, followed by a redox process
to give the alkyne radical, which would undergo further transformation to afford the
final product (Scheme 3.3, path B).
General Procedure for KI-Mediated Homo-Coupling Reactions of Haloalkynes:
Haloalkyne (1 mmol) and KI (3 mmol) in DMF (2 mL) were stirred at 120 °C for
12 h in a Schlenk tube (25 mL). Water (8 mL) was added after the completion of the
KI (3 equiv)
R X R R
DMF, 120 oC
R = alkyl, aryl 23 examples
X = Br, I 50-99% yields
R Br
I
R I
path A path B
R + I2
R + I
R + I
R R
Scheme 3.3 KI-mediated homo-coupling reactions of haloalkynes
reaction, the aqueous solution was extracted with diethyl ether (15 mL × 3), and the
combined extracts were dried with anhydrous MgSO4, filtered, and concentrated
under reduced pressure. The residue was purified by silica gel column chro-
matography to give the corresponding 1,3-diyne.
C(sp)–C(sp) Cross-Coupling
Compared to symmetrical 1,3-diyne compounds, the synthesis of unsymmetrical

1,3-diynes is rather difficult, due to the competition of homo-coupling reaction.
Among the methods for the synthesis of unsymmetrical 1,3-diynes,
Cadiot-Chodkiewicz cross-coupling reaction is one of the most representative
examples [11]. In 2007, Jiang’s group documented a mild and environmentally
friendly method for the Cu-catalyzed Cadiot-Chodkiewicz coupling of bro-
moalkynols with terminal acetylenes in scCO2 utilizing NaOAc as base (Table 3.1)
[12]. Methanol, as a co-solvent, could improve the dissolution of inorganic salts in
scCO2 and facilitate the reaction rate. This new cross-coupling reaction system not
only tolerated a wide range of functional groups to deliver diverse unsymmetrically
substituted 1,3-diynes, but also avoided the employment of amine. However,
experiment results revealed that this transformation was sensitive to the pressure of
scCO2 and high reaction temperature.
General Procedure for Cu-Catalyzed Cross-Coupling Reactions of
Bromoalkynols: CuCl (5 mol%), AcONa (1.5 mmol), MeOH (1 mL), bromoalkyne
(1 mmol) and alkyne (1.2 mmol) were added to an autoclave vessel (15 mL) in
Table 3.1 Cu-catalyzed cross-coupling reactions of bromoalkynols
CuCl (5 mol%)
NaOAc (1.5 equiv)
R 1
Br + R 2 R1 R2
MeOH, scCO2 (9 MPa)
40 oC
R1 = alkyl 21 examples
R2 = alkyl, aryl, ester 42-93% yields
HO
HO HO
CO2Et nC6H13
85% 87% 83%
CuFe2O4 (5 mol%)
O Cs2CO3, DMC
R X + Ar B R Ar
O 8 h, reflux
11 examples
X = Br, Cl Recyclable CuFe2O4 Nanoparticle
46-84% yields
Ph MeO Ph Ph
S
84%
82% 82%
Scheme 3.4 CuFe2O4 nanoparticle catalyzed cross-coupling reactions of haloalkynes
sequence. Liquid CO2 was pumped into the autoclave by a cooling pump until the
desired pressure was reached then the autoclave was heated in an oil bath under
magnetic stirring for the desired reaction time. After the reaction was completed,
the autoclave was allowed to cool to 0 °C and CO2 was vented. The residue was
extracted with Et2O (20 mL). The extract was filtered and concentrated under
reduced pressure to give a residue that was purified by chromatography on a silica
gel column using light PE-EtOAc as eluent.
Later in 2014, Ranu and co-workers developed a novel protocol for C(sp)–C(sp)
cross-coupling of haloalkynes with pinacol ester of alkynyl boronic acid in dime-
thyl carbonate (DMC) using a commercially available and magnetically separable
CuFe2O4 nanoparticle catalyst. The reaction has a broad substrate scope and tol-
erates diverse functional groups. Importantly, the CuFe2O4 nanoparticle catalyst
was recycled more than 10 times with marginal loss of activity in subsequent runs
(Scheme 3.4) [13].
General Procedure for CuFe2O4 Nanoparticle Catalyzed Cross-Coupling
Reactions of Haloalkynes: A suspension of haloalkyne (1 mmol), pinacol ester of
Pd(dba)2 (4 mol%)/L (4 mol%)

NEt3 (2 equiv), CuI (2 mol%)
R1 Br + R2 R1 R2
DMF, rt, 2-9 h
R1 = alkyl, aryl 16 examples
R2 = alkyl, aryl PPh2
77-99% yields
L O
R1 R2 Pd0Ln R1 Br
R1 PdII Ln R1 PdII Ln
Br
R2
CuBr R2 Cu
NEt3 + R2 HNEt3Br
Scheme 3.5 Ligand accelerated Pd-catalyzed cross-coupling reactions of bromoalkynes
alkynelboronic acid (1.5 mmol), Cs2CO3 (2 mmol), and CuFe2O4 (5 mol%) in

DMC (5 mL) was stirred at 100 °C (oil bath temperature) for 8 h under argon. The
reaction mixture was allowed to cool and extracted with ethyl acetate (20 mL × 3).
The organic extracts were washed with brine, dried with anhydrous Na2SO4, fil-
tered, and concentrated under reduced pressure. The product was obtained by flash
column chromatography.
Except for Cu catalysis, Pd complexes also serve as a powerful catalysts to con-
struct several conjugated diynes [14]. However, the competitive homo-coupling
process is still the major challenge in Pd-catalyzed C(sp)–C(sp) cross-coupling
reactions. In 2008, Lei’s group [15] reported an efficient method to synthesize
unsymmetrical 1,3-diynes which was promoted by Pd(dba)2 with a phosphine-olefin
ligand L (Scheme 3.5). This protocol realized the cross-coupling reaction of a wide
spectrum of terminal alkynes and haloalkynes, affording the corresponding conju-
gated diynes in good to excellent yields with high selectivity. Notably, one-pot
synthesis of symmetrical and unsymmetrical triynes was also achieved. Mechanistic
investigations indicated that the phosphine-olefin ligand could accelerate the
reductive elimination process in the catalytic cycle, thereby enhancing the selectivity.
General Procedure for Ligand Accelerated Pd-Catalyzed Cross-Coupling

Reactions of Bromoalkynes: To an oven-dried Schlenk tube with a magnetic stir bar
were added Pd(dba)2 (4 mol%), L ligand (4 mol%), and CuI (2 mol%). DMF
(1 mL) was added via a syringe. The system was vacuumed with an oil pump at 0 °
C and filled with nitrogen, and this procedure was repeated five times. After the
mixture was stirred under nitrogen for about 10 min, alkyne (0.6 mmol) was added
via a microliter and stirred for another 5 min. 1-Bromoalkyne (0.5 mmol) was
added last via a microliter syringe. The system was stirred at room temperature for
10 h. Upon completion, brine (4 mL) was added, and the mixture was extracted by
ethyl acetate (3 mL × 3), and the combined extracts were dried with anhydrous
MgSO4, filtered, and concentrated under reduced pressure. The product was
obtained by flash column chromatography.
Later in 2012, Lei and co-workers developed a more efficient Pd0-catalyzed C
(sp)–C(sp) cross-coupling reaction of terminal alkynes with bromoalkynes.
Interestingly, the reaction could run at 100 mmol scale, and more than 99 % of the
cross-coupling product was obtained without any bromoalkyne homo-coupled
by-product. The key to the success of this transformation was the utilization of
TBAB (tetrabutylammonium bromide) as a stabilizer, which could prevent the
aggregation and precipitation of palladium catalyst. Even when the catalyst loading
was reduced to 0.01 mol%, the reaction could still proceed efficiently, and the
catalyst was kept active. Kinetic studies indicated that the reaction rate was not first
order to Pd catalyst via in situ IR spectroscopy, and only part of the Pd species was
employed to catalyze this C(sp)–C(sp) cross-coupling reaction. Importantly, pal-
ladium nanoparticles were observed in this reaction (Scheme 3.6) [16].
General Procedure for TBAB Stabilized Pd-Catalyzed Cross-Coupling
Reactions of Bromoalkynes: A mixture of haloalkyne (1 mmol), terminal alkyne
(1.5 mmol), TBAB (0.3 mol%), and CuI (0.2 mol%) in iPr2NH (5 mL) was stirred
under N2 at 70 °C for 5 min. Then Pd(OAc)2 (0.01 mol%) was added in one
Pd(OAc)2 (0.01 mol%)

TBAB (0.3 mol%), CuI (0.2 mol%)
R 1
Br + R 2 R1 R2
iPr2NH, 70 oC, 12 h
R1 = alkyl, aryl 22 examples
R2 = alkyl, aryl up to 100 mmol scale 52-99% yields
HO HO O HO
S Me NH2
O N
99% 99% 85%
HO HO
O Ph CN
HN Ts O
52% 59% 85%
Scheme 3.6 TBAB stabilized Pd-catalyzed cross-coupling reactions of bromoalkynes

portion. After reaction completion, as indicated by TLC and GC, the mixture was
quenched with diluted hydrochloric acid (4 mL, 2 M), and the solution was
extracted with ethyl acetate (15 mL × 3). The organic layers were combined and
dried over sodium sulfate. The pure product was obtained by flash column chro-
matography on silica gel.
3.1.1.2 Construction of C(sp)–C(sp2) Bond
Functionalized cyclic and acyclic enynes are all-pervading subunits in a wide range
of natural products, functional materials and bioactive compounds [17]. To this
regard, the development of efficient and practical methods for the construction of
conjugated enyne molecules has become the subject of intensive investigation in the
area of synthetic and medicinal chemistry.
C(sp)–C(sp2) Cross-Coupling
In 1985, Suzuki and co-workers reported the synthesis of alkyenynes via

palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalky-
nes (Scheme 3.7) [18]. This reaction was stereo- and regiospecifically, and the
Pd(PPh3)4 (1 mol%) R2
R2 MeONa (1.4 equiv)
3
+ Br R
R1 B(Sia)2 Benzene, reflux R1
3
5 examples R
53-98% yields
R2 R3 Pd0L4 R3 Br
1
R
L
R1
R3 PdII Br
L R2
R3 PdII 2 L
L MeONa
MeOB(Sia)2 L NaBr
R3 PdII OMe
R2
B(Sia)2 L
R1 3
Scheme 3.7 Cross-coupling reaction of 1-alkenylboranes with bromoalkynes

configurations of both the starting alkynylboranes and bromoalkynes were retained.

Mechanistic studies indicated that the transmetalation between an alkynylborane
and an alkoxypalladium(II) complex 3 generated through the metathetical dis-
placement of a halogen atom from the intermediate 2 with the base. Later, the
cross-coupling reactions of haloalkynes with activated alkenes have been broadly
investigated, such as alkenylboronic acid [19–21]. oragnozinc reagents [22, 23],
vinylstannanes [24–26]. Grignard reagents [27], vinylzirconocene [28, 29], and
vinylsiloxanes [30].
General Procedure for Palladium Catalyzed Cross-Coupling Reaction of 1-
Alkenylboranes with Bromoalkynes: A flask (50 mL) was charged with Pd(PPh3)4
(1 mol%), dry benzene (12 mL), and bromoalkyne (5 mmol) under a nitrogen
atmosphere. The reaction mixture was stirred for 30 min at room temperature, and
to the solution were added alkenylborane (6 mmol) and MeONa (7 mmol, 1 M in
MeOH). The reaction mixture was heated under reflux for 2 h and then treated with
aqueous NaOH (1.8 mL, 3 M solution) and H2O2 (1.8 mL of a 30 % solution) for
1.5 h at room temperature to remove the unreacted alkenylborane. The product was
extracted with hexane and dried over MgSO4. After the removal of the solvent, the
enyne product was purified by distillation.
Alternatively, the Sonogashira coupling, the cross-coupling reaction between
vinyl halides and terminal alkynes also represents one of the most widely used
strategies achieving the synthesis of functionalized enynes [31]. In this context, the
development of “Inverse Sonogashira Coupling”, the term which was first intro-
duced by Trofimov [32], has attracted more and more attention (Scheme 3.8) [33].
It stands as a complementary strategy for the synthesis of aryl/heteroaryl alkynes
through the direct alkynylation of unreactive C(sp2)–H bonds with readily available
haloalkynes. In 1992, Kalinin and coworkers firstly reported this type of alkyny-
lation reaction with a stoichiometric amount of CuI salt [34]. Later, Trofimov and
co-workers devoted great efforts in this area [35–42]. However, the major break-
through was achieved until 2007, as the first example of a transition metal-catalyzed
direct alkynylation of electron-rich N-fused heterocycles was promulgated by
Gevorgyan’s group (Scheme 3.9) [43]. A wide spectrum of indolizine,
pyrroloisoquinoline, pyrroloquinoline, and pyrrolooxazole derivatives could be
regioselectively alkynylated with different substituted bromoalkynes in the presence
Scheme 3.8 Development of

“Inverse Sonogashira Sonogashira Coupling Inverse Sonogashira Coupling
Coupling”
Ar/ X + H R Ar/ H + X R
Het Het
[M] or [TM] [M] or [TM]
Ar/ R Ar/ R
Het Het
Pd(PPh3)4 (3 mol%)
H KOAc (2 equiv) R
N + Br R
PhMe, 30-80 C o N
17 examples
R = Ar, alkyneyl, alkyl, SiMe3, CO2Et
50-90% yields
R Pd0Ln R Br
N
R PdIILnBr Ar PdIILnBr
Pd II 5
N 4
Ln
R
H
HBr H Base N
PdII
N
Ln R
Scheme 3.9 Pd-catalyzed alkynylation of N-fused heterocycles
of Pd catalyst. The alkynylpalladium intermediate 4, which is essential for con-

ceptual advance, generated through Pd0 catalyst oxidative addition into the C–Br
bond of bromoalkyne, exhibited the similar reactivity to that of arylpalladium
species 5, which is well known to undergo an electrophilic pathway in the process
of indolizine arylation. Subsequently, Gu [44], Chang [45], Jiang [46, 47], and Loh
[48] documented different cross-coupling partners with haloalkynes under palla-
dium catalysis.
General Procedure for Pd-Catalyzed Alkynylation of N-Fused Heterocycles: In a
glovebox under nitrogen atmosphere, to a Wheaton microreactor (5 mL) equipped
with a spin vane and screw cap with a polytetrafluoroethylene (PTFE) faced sili-
cone septum under nitrogen atmosphere were added heterocyclic substrate (1
equiv), Pd(PPh3)2Cl2 (3–5 mol%) and KOAc (2 equiv). The microreactor was
removed from the glovebox, bromoalkyne (1.3–1.8 equiv) and anhydrous toluene
(0.001–0.010 M) were successively added and the mixture was stirred until com-
pletion (as monitored by TLC and/or GC/MS). The solvent was removed under
reduced pressure and the residue was purified using flash-column chromatography
using hexane or hexanes/ethylacetate combination as eluent to afford pure
alkynyl-heterocycles.
Despite palladium catalysis, Piguel [49] reported a more efficient general pro-
cedure for the direct alkynylation of various heterocycles with copper-catalysis. The
author found out that the success of the copper bromide/dimethyl sulfide complex
CuBr.SMe2 (15 mol%)

N
X
DPEPhos (15 mol%) X N
+ Br R2 R2
O LiOtBu (2 equiv) 1 O
R
R1 dioxane, 120 oC, 1 h
X = C, N 20 examples
R2 = aryl, alkyneyl, alkyl, Si(iPr)3 26-90% yields
N N N
Ph
Ph O Ph O N Ph O Ph
89% 73% 73%
N N N N
Si(iPr)3 Ph
Ph O Ph Ph O Ph O
26% 84% 71%
Scheme 3.10 Copper-catalyzed alkynylation of azoles
lied in the better solubility compared that with the uncomplexed copper bromide,
which allowed it to coordinate immediately in the reaction medium. This method
did not need high dilution reaction condition. Especially, the minimal cost and
toxicity of copper catalyst could tolerate various oxazoles with different electron
property and structural diversity, and gave the coupling product in good yields
(Scheme 3.10). Notably, the azoles are with high pKa values (>30), while the
carbon-halo bond of the substrate could survive under the standard reaction con-
ditions. Additionally, the structure of the product was unambiguously confirmed by
single-crystal X-ray diffraction analysis.
General Procedure for Copper-Catalyzed Alkynylation of Azoles: A flame dried
tube under argon was charged with azole (0.69 mmol), CuBr·SMe2 (15 mol%),
DPE-Phos (15 mol%), tBuLi (1.38 mmol). Then bromoalkyne (1.38 mmol) was
diluted into dioxane (2 mL) and the solution was added to the medium. The tube
was sealed with Teflon cap and put in a pre-heated oil bath at 120 °C for 1 h. The
reaction mixture was diluted with ethyl acetate and water was added. This mixture
was extracted with ethyl acetate and the combined organic layers were put together
and dried over MgSO4. Solvents were removed under reduced pressure and the
crude was purified by flash chromatography on silica gel to afford the desired
product.
Based on the experimental results and previous literatures [50, 51], the authors
proposed the possible reaction mechanism as illustrated in Scheme 3.11. Firstly, the
deprotonation of oxazole lithium base, followed by lithium-copper transmetallation
to generate CuI intermediate 6. Subsequently, the oxidative addition of 6 to bro-
moalkyne gave the four-coordinated CuIII complex 7. Finally, the reductive elim-
ination led to the desired alkynylated product, and regenerated the catalytic CuI
N
+ LiOtBu
N P 1 O
I
R
R2 Br Cu
O P tBuOH + LiBr
R1
Li
N N P
P R1 CuI
N R1 O O
CuI P
N N
P O 6 P O
R1 Br R1
O CuIII
P 8 R1
oxidation
R2
R1 O O R1
7
2
Br R
N 9 N
Scheme 3.11 Proposed reaction mechanism
species. Undoubtedly, the formation of CuIII complex 7 would compete with

activation of another oxaole, which would deliver the bis(oxazolte) CuI species 8,
and afforded the undersired bis(oxazole) dimer 9. Importantly, the steric hindrance
of the copper center favored the less sterically demanding haloalkyne, thus 7 was
formed preferentially. Finally, due to the solubility of dimethylsulfide complex and
the bulky steric hindrance effect of the ligand, the catalytic cycle was driven
towards the formation of the alkynylated product.
Later, Miura [52] and Das [53] independently realized the copper-catalyzed
alkynylation of 1,3,4-oxadiazoles. In the mean time, other transition metals, such as
nickel, were found to be suitable catalysts for the inverse Sonogashira coupling
reactions of haloalkynes [54]. These achievements in the area of direct alkynylation
reactions involving haloalkyne reagents open up new exciting opportunities for the
functionalization of diverse C(sp2)–H bonds.
The cyclization of alkynes bearing proximate nucleophilic centers promoted by
organopalladium complexes is an effective strategy for heterocyclic ring synthesis
[55]. This chemistry provides a direct method to the construction of functionalized
cycles through the regio- and stereoselective addition of a nucleophile to the
carbon-carbon triple bond with the generation of a vinylpalladium complex, which
could proceed diverse transformations (Scheme 3.12). Taking the advantages of this
strategy, Larock [56], Cacchi [57], and Yorimitsu [58] independently demonstrated
that nucleophilic addition triggered cross-coupling reaction of haloalkynes to
synthesize 3,4-disubstituted isoquinolines, 3-alkynylindoles and 1,2-disubstituted
cyclopentenes, respectively.
Alkynylation Reactions
Compared to cross coupling reactions, electrophilic ethynylation of carbon nucle-

ophiles is another attractive methodology to construct C(sp)–C(sp2) bonds. In 2002,
Another random document with
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eight thousand merks per annum (£444, 8s. 10d.⅔), she conceived
that four thousand was the least that could be modified for her
behalf, along with the mansion of Duncrub, which had been assigned
to her as her jointure-house.
The Lords of the Council ordained that Lord Rollo should be cited
for a particular day, and that for the time past, and till that day, the
tenants should pay her ladyship a thousand pounds Scots, she
meanwhile enjoying the use of Duncrub House. Lord Rollo, failing to
appear on the day cited, was declared rebel, and the lady’s petition
was at the same time complied with in its whole extent.[173]
William Murray, tavern-keeper in the 1696. Jan.
Canongate, was again a prisoner on account
of an offensive news-letter. He had suffered close imprisonment for
twenty-one weeks, till ‘his health is so far decayed, that, if he were
any longer where he is, the recovery thereof will be absolutely
desperate.’ His house having been shut up by the magistrates, his
liquors and furniture were spoiled, and ‘his poor wife and family
exposed to the greatest extremity and hazard of being starved for
cold and hunger in this season of the year.’ He represented to the
Privy Council that he was willing to be tried for any crime that could
be laid to his charge. ‘Ane Englishman’s directing,’ however, ‘of ane
news-letter to him was neither a crime nor any fault of his.... In case
there was anything unwarrantable in the letter, the postmaster was
obliged in duty to have suppressed the same, after he had read and
perused it.’ His having, on the contrary, delivered it, ‘after he had
read and perused it,’ was ‘sufficient to put him in bonâ fide to believe
that the letter might thereafter be made patent.’
Murray went on to say that ‘this summar usage of himself and his
poor family, being far above the greatest severity that ever was
inflicted by their Lordships or any sovereign court of the nation,
must be conceived to be illegal, arbitrary, and unwarrantable, and
contrair both to the claim of right and established laws and
inviolable practice of the nation.’
The Council did so far grant grace to Murray as to order him out of
jail, but to be banished from Lothian, with certification that, if found
in those bounds after ten days, he should be taken off to the
plantations.[174]
The imbecile Laird of Drum was recently Jan. 16.
dead, and the lady who had intruded herself
into the position of his wife—Marjory Forbes by name—professed a
strong conviction that she would ere long become the mother of an
heir to the estate. For this consummation, however, it was necessary
that she should have fair-play, and this she was not likely to get.
Alexander Irvine of Murtle, heir of tailzie to the estate in default of
issue of the late laird, had equally strong convictions regarding the
hopes which Lady Drum asserted herself to entertain. He deemed
himself entitled to take immediate possession of the castle, while
Marjory, on her part, was resolved to remain there till her expected
accouchement. Here arose a fine case of 1696.
contending views regarding a goodly
succession, worthy to be worked out in the best style of the country
and the time.
Marjory duly applied to the Privy Council with a representation of
her circumstances, and of the savage dealings of Murtle. When her
condition and hopes were first spoken of some months ago,
‘Alexander Irvine, pretended heir of tailzie to the estate of Drum’—so
she designated him—‘used all methods in his power to occasion her
abortion, particularly by such representations to the Privy Council as
no woman of spirit, in her condition, could safely bear.’ When her
husband died, and while his corpse lay in the house, Murtle
‘convocat a band of armed men to the number of twenty or thirty,
with swords, guns, spears, fore-hammers, axes, and others, and
under silence of night did barbarously assault the house of Drum,
scaled the walls, broke up the gates and doors, teared off the locks,
and so far possessed themselves of all the rooms, that the lady is
confined in a most miserable condition in a remote, obscure, narrow
corner, and no access allowed to her but at ane indecent and most
inconvenient back-entry, not only in hazard of abortion, but under
fear of being murdered by the said outrageous band of men, who
carouse and roar night and day to her great disturbance.’
The lady petitioned that she should be left unmolested till it should
appear in March next whether she was to bring forth an heir; and the
Lords gave orders to that effect. Soon after, on hearing
representations from both parties, four ladies—namely, the spouses
of Alexander Walker and John Watson of Aberdeen, on Murtle’s
part, and the wife of Count Leslie of Balquhain and the Lady
Pitfoddels, on Lady Drum’s part—were appointed to reside with her
ladyship till her delivery, Murtle meanwhile keeping away from the
house.[175]
If I am to believe Mr Burke, Marjory proved to have been under a
fond illusion, and as even a woman’s tenacity must sometimes give
way, especially before decrees of law, I fear that Murtle would have
her drummed out of that fine old Aberdeenshire château on the
ensuing 1st of April.
Sir Robert Grierson of Lagg, the notable ‘persecutor,’ who had

been not a little persecuted himself after the Revolution as a person
dangerous to the new government, was now in trouble on a different
score. He was accused of the crimes of 1696.
‘clipping of good money and coining of false
money, and vending the samen when clipped and coined,’ inferring
the forfeiture of life, land, and goods.
It appears that Sir Robert had let his house of Rockhill to a person
named John Shochon, who represented himself as a gunsmith
speculating in new modes of casting lead shot and stamping of cloth.
A cloth-stamping work he had actually established at Rockhill, and
he kept there also many engraving tools which he had occasion to use
in the course of his business. But a suspicion of clipping and coining
having arisen, a search was made in the house, and though no false
or clipped coin was found, the king’s advocate deemed it proper to
prosecute both Shochon and his landlord on the above charge.
The two cases were brought forward June 22.
separately at the Court of Justiciary, and
gave rise to protracted proceedings; but the result was, that Sir
Robert and Shochon appeared to have been denounced by enemies
who, from ignorance, were unable to understand the real character of
their operations, and the prosecution broke down before any assize
had been called.[176]
Shochon was residing in Edinburgh in 1700, and then petitioned
parliament for encouragement to a manufactory of arras, according
to a new method invented by him, ‘the ground whereof is linen, and
the pictures thereof woollen, of all sorts of curious colours, figures,
and pictures.’[177]
‘Lagg’—who had drowned religious women at stakes on the sands
of Wigton—had the fortune to survive to a comparatively civilised
age. He died in very advanced life, at Dumfries, about the close of
1733.
Some printed copies of certain ‘popish Apr. 10.
books’—namely, The Exposition of the True
Doctrine of the Catholic Church in Matters of Controversy, An
Answer to M. Dereden’s Funeral of the Mass, and The Question of
Questions, which is, Who ought to be our Judges in all Differences
in Religion?—having been seized upon in a private house in
Edinburgh, and carried to the lodging of Sir Robert Chiesley, lord
provost of the city, the Privy Council authorised Sir Robert ‘to cause
burn the said books in the back-close of the town council by the hand
of the common executioner, until they be consumed to ashes.’
Six months later, the Privy Council 1696.
ordered a search of the booksellers’ shops in
Edinburgh for books ‘atheistical, erroneous, profane, or vicious.’
We find the cause of this order in the fact, that John Fraser, book-
keeper to Alexander Innes, factor, was before the Council on a charge
from the Lord Advocate of having had the boldness, some day in the
three preceding months, ‘to deny, impugn, argue, or reason against
the being of a God;’ also he had denied the immortality of the soul,
and the existence of a devil, and ridiculed the divine authority of the
Scriptures, ‘affirming they were only made to frighten folks and keep
them in order.’
Fraser appeared to answer this charge, which he did by declaring
himself of quite a contrary strain of opinions, as became the son of
one who had suffered much for religion’s sake in the late reigns. He
had only, on one particular evening, when in company with the
simple couple with whom he lived, recounted the opinions he had
seen stated in a book entitled Oracles of Reason, by Charles Blunt;
not adverting to the likelihood of these persons misunderstanding
the opinions as his own. He professed the greatest regret for what he
had done, and for the scandal he had given to holy men, and threw
himself upon their Lordships’ clemency, calling them to observe that,
by the late act of parliament, the first such offence may be expiated
by giving public satisfaction for removing the scandal.
The Lords found it sufficiently proven, that Fraser had argued
against the being of a God, the persons of the Trinity, the immortality
of the soul, and the authority of the Scriptures, and ordained him to
remain a prisoner ‘until he make his application to the presbytery of
Edinburgh, and give public satisfaction in sackcloth at the parish kirk
where the said crime was committed.’ Having done his penance to
the satisfaction of the presbytery, he was liberated on the 25th of
February.
The Council at the same time ordered the booksellers of Edinburgh
to give in exact catalogues of the books they had for sale in their
shops, under certification that all they did not include should be
confiscated for the public use.[178]
In the austerity of feeling which reigned Apr. 15.

through the Presbyterian Church on its re-
establishment, there had been but little 1696.
disposition to assume a clerical uniform, or
any peculiar pulpit vestments. It is reported, that when the noble
commissioner of one of the first General Assemblies was found fault
with by the brethren for wearing a scarlet cloak, he told them he
thought it as indecent for them to appear in gray cloaks and cravats.
[179]
When Mr Calamy visited Scotland in 1709, he was surprised to
find the clergy generally preaching in ‘neckcloths and coloured
cloaks.’[180] We find at the date here marginally noted, that the synod
of Dumfries was anxious to see a reform in these respects. ‘The
synod’—so runs their record—‘considering that it’s a thing very
decent and suitable, so it hath been the practice of ministers in this
kirk formerly, to wear black gowns in the pulpit, and for ordinary to
make use of bands, do therefore, by their act, recommend it to all
their brethren within their bounds to keep up that laudable custome,
and to study gravitie in their apparel and deportment every manner
of way.’
From a poem of this time, in which a Fife laird, returned from the
grave, gives his sentiments on old and new manners, we learn that
formerly
We had no garments in our land,
But what were spun by th’ goodwife’s hand,
No drap-de-berry, cloths of seal,
No stuffs ingrained in cochineal;
No plush, no tissue, cramosie,
No China, Turkey, taffety;
No proud Pyropus, paragon,
Or Chackarally there was none;
No figurata, water shamlet,
No Bishop sattin, or silk camblet;
No cloth of gold or beaver hats,
· · · · ·
No windy-flourished flying feathers,

No sweet, permusted shambo leathers, &c.
And things were on an equally plain and simple footing with the
ladies; whereas now they invent a thousand toys and vanities—
As scarfs, shefroas, tuffs, and rings,
Fairdings, facings, and powderings,
Rebats, ribands, bands, and ruffs,
Lapbends, shagbands, cuffs, and muffs;
Folding o’erlays, pearling sprigs,
Atries, fardingales, periwigs;
Hats, hoods, wires, and also kells,
Washing balls and perfuming smells;
French gowns cut and double-banded,
Jet rings to make her pleasant-handed;
A fan, a feather, bracelets, gloves—
All new-come busks she dearly loves.[181]
The spirit which dictated these lines was 1696.

one which in those days forced its way into
the legislation of the country. In September 1696, an overture was
read before parliament ‘for ane constant fashion of clothes for men,
and another for ane constant fashion of clothes for women.’ What
came of this does not appear; but two years later, the parliament
took under consideration an act for restraining expenses of apparel.
There was a debate as to whether the prohibition of gold and silver
on clothes should be extended to horse-furniture, and carried that it
should. Some one put to the vote whether gold and silver lace
manufactured within the kingdom might not be allowed, and the
result was for the negative. It was a painful starving-time, and men
seem to have felt that, while so many were wretched, it was impious
for others to indulge in expensive vanities of attire. The act, passed
on the 30th August 1698, discharged the wearing of ‘any clothes,
stuffs, ribbons, fringes, tracing, loops, agreements, buttons, made of
silver or gold thread, wire, or philagram.’
Two young men, Matthew M‘Kail, son of Apr.

an advocate of the same name, and Mr
William Trent, writer, hitherto intimate friends, quarrelled about a
trifling matter, and resolved to fight a duel. Accompanied by John
Veitch, son of John Veitch, ‘presentee of the signator,’ and William
Drummond, son of Logie Drummond, youths scarcely out of their
minority, they went two days after—a Sunday having intervened—to
the park of Holyrood Palace, and there fought—it does not appear
with what weapons—but both were slain on the spot; after which the
seconds absconded.[182]
A preacher named John Hepburn, who July.

had been called to the parish of Urr in
Galloway, before the regular establishment of the church in 1690,
continued ever since to minister there and in the neighbouring
parish of Kirkgunzeon, without any proper authority. Enjoying the
favour of an earnest, simple people, and cherishing scruples about
the established church, he maintained his 1696.
ground for several years, in defiance of all
that presbyteries, synods, and general assemblies could do for his
suppression. Holding a fast amongst his own people (June 25, 1696),
he was interrupted by a deputation from the presbytery of Dumfries,
but nevertheless persisted in preaching to his people in the open air,
though, as far as appears, without any outward disorderliness. It
affords a curious idea of the new posture of Presbyterianism in
Scotland, that one of the deputation was Mr William Veitch, a noted
sufferer for opinion in the late reign.
The Privy Council took up this affair as a scandalous tumult and
riot, and had Mr Hepburn brought before them, and condemned to
give bond under a large forfeiture that he would henceforth live in
the town of Brechin and within two miles of the same—a place where
they of course calculated that he could do no harm, the inhabitants
being so generally Episcopalian. Meanwhile, he was laid up in the
Old Tolbooth, and kept there for nearly a month. There were people
who wished to get in to hear him. There were individuals amongst
his fellow-prisoners also anxious to listen to his ministrations. The
Council denied the necessary permission. We hear, however, of Mr
Hepburn preaching every Sunday from a window of his prison to the
people in the street. He was then conducted to Stirling Castle, and
kept in durance there for several months. It was three years before he
was enabled to return to his Galloway flock.[183] The whole story
reads like a bit of the history of the reign of Charles II. misplaced,
with presbyteries for actors instead of prelates.
A crew of English, Scots, and foreigners, Sep.

under an Englishman named Henry Evory
or Bridgman, had seized a ship of forty-six guns at Corunna, and had
commenced in her a piratical career throughout the seas of India and
Persia. Having finally left their ship in the isle of Providence, these
pirates had made their way to Scotland, and there dispersed, hoping
thus to escape the vengeance of the laws which they had outraged.
The Privy Council issued a proclamation, commanding all officers
whatsoever in the kingdom to be diligent in trying to catch the
pirates, ‘who may probably be known and discovered by the great
quantities of Persian and Indian gold and silver which they have with
them,’ a hundred pounds of reward being 1696.
offered for apprehending Bridgman, and
fifty for each of the others.[184]
Since the Reformation, there had been Sep.

various public decrees for the establishment
of schools throughout Scotland; but they had been very partially
successful in their object, and many parishes continued to be without
any stated means of instruction for the young. The Presbyterian or
ultra-Protestant party, sensible how important an ability to read the
Scriptures was for keeping up a power in the people to resist the
pretensions of the Romish Church, had always, on this account, been
favourable to the maintenance of schools whereby the entire people
might be instructed. Now, that they were placed securely in
ascendency, they took the opportunity to obtain a parliamentary
enactment ‘for settling of schools,’ by virtue of which it was ordered
that the heritors (landowners) of each parish in the realm should
‘meet and provide a commodious house for a school, and settle and
modify a salary to a schoolmaster, which shall not be under one
hundred nor above two hundred merks [£5, 11s. 1d.⅓ and £11, 2s.
2d.⅔].’[185] It was thus made a duty incidental to the possession of
land in each parish, that a school and schoolmaster should be
maintained, and that the poorest poor should be taught; and, in
point of fact, the community of Scotland became thus assured of
access to education, excepting in the Highlands, where the vast
extent of the parishes and other circumstances interfered to make
the act inoperative. The history of the commencement of our
parochial school establishment occupies but a page in this record;
but the effects of the measure in promoting the economic and moral
interests of the Scottish people are indefinite. It would be wrong to
attribute to that act solely, as has sometimes been done, all the credit
which the nation has attained in arts, in commerce, in moral
elevation, and in general culture. But certainly the native energies
have been developed, and the national moral character dignified, to a
marked extent, through the means of these parish schools—an effect
the more conspicuous and unmistakable from the fact of there
having been no similar institution to improve the mass of society in
the sister-kingdom.
It is a rather whimsical association of Oct. 15.

ideas, that Sir David Dunbar, the hero of the
sad story of the Bride of Baldoon[186]—the 1696.
bridegroom in the case—was an active
improver of the wretched rural economy of his day. Some years
before his unfortunate death in 1682, he had formed the noted park
of Baldoon, for the rearing of a superior breed of cattle, with a view
to the demands of the market in England. It was, as far as I can learn,
the first effort of the kind made in Scotland, and the example was not
without imitation in various parts of the southwestern province of
Scotland.
Andro Sympson, in his gossiping Description of Galloway, written
before the Revolution, speaks of the park of Baldoon as a rich
pastoral domain, of two and a half miles in length and one and a half
in breadth, to the south of the river Blednoch. It ‘can,’ he says, ‘keep
in it, winter and summer, about a thousand bestial, part whereof he
[Sir David Dunbar] buys from the country, and grazeth there all
winter, other part whereof is his own breed; for he hath nearly two
hundred milch kine, which for the most part have calves yearly. He
buys also in the summer-time from the country many bestial, oxen
for the most part, which he keeps till August or September; so that
yearly he either sells at home to drovers, or sends to St Faith’s, and
other fairs in England, about eighteen or twenty score of bestial.
Those of his own breed at four year old are very large; yea, so large,
that, in August or September 1682, nine-and-fifty of that sort, which
would have yielded betwixt five and six pound sterling the piece,
were seized upon in England for Irish cattle; and because the person
to whom they were intrusted had not witnesses there ready at the
precise hour to swear that they were seen calved in Scotland, they
were, by sentence of Sir J. L. and some others, who knew well
enough that they were bred in Scotland, knocked on the head and
killed.’
The estate of Baldoon having, by the marriage of the heiress, Mary
Dunbar, come into the possession of Lord Basil Hamilton, a younger
son of the Duke and Duchess of Hamilton, we now find that young
nobleman petitioning the Privy Council for permission to import
from Ireland ‘six score young cows of the largest breed for making up
his lordship’s stock in the park of Baldoon,’ he giving security that he
would import no more, and employ these for no other end.[187]
The example of the Baldoon park was 1696.
followed by the Laird of Lochnaw and other
great proprietors, and the growing importance of the cattle-rearing
trade of Galloway is soon after marked by a demand for a road
whereby the stock might be driven to the English market. In June
1697, the matter came before the Privy Council. It was represented
that, while there was a customary way between the burgh of New
Galloway and Dumfries, there was no defined or made road. It was
the line of passage taken by immense herds of cattle which were
continually passing from the green pastures of the Galloway hills into
England—a branch of economy held to be the main support of the
inhabitants of the district, and the grand source of its rents. Droves
of cattle are, however, apt to be troublesome to the owners and
tenants of the grounds through or near which they pass; and such
was the case here. ‘Several debates have happened of late in the
passage of droves from New Galloway to Dumfries, the country
people endeavouring by violence to stop the droves, and impose
illegal exactions of money upon the cattle, to the great damage of the
trade; whereby also riots and bloodsheds have been occasioned,
which had gone greater length, if those who were employed to carry
up the cattle had not managed with great moderation and prudence.’
On a petition from the great landlords of the district, James Earl of
Galloway, Lord Basil Hamilton, Alexander Viscount of Kenmure,
John Viscount of Stair, Sir Andrew Agnew of Lochnaw, Sir Charles
Hay of Park, &c., a commission was appointed by the Privy Council
‘to make and mark a highway for droves frae New Galloway to
Dumfries,’ holding ‘the high and accustomed travelling way betwixt
the said two burghs.’[188]
Amongst Sir David Dunbar’s imitators, it appears that we have to
class Sir George Campbell of Cessnock, in Ayrshire, so noted for his
sufferings under the late reign. The parks of Cessnock had formerly
been furnished with ‘ane brood of great cattle’ and a superior breed
of horses, both from Ireland; but, on the unjust forfeiture of the
estate, the stock had been taken away and destroyed, so that it was
‘entirely decayed out of that country.’ Sir George, to whom the estate
had been restored at the Revolution, obtained, in March 1697,
permission from the Privy Council ‘to import from Ireland sixty cows
and bulls, thretty-six horses and mares, and six score of sheep, for
plenishing of his park.’ Soon after, the 1696.
Council recalled the permission for the
sheep.
The rolls of parliament and the books of Oct.

the Privy Council contain about this time
abundant proofs of the tendency to manufacturing enterprise. Sir
John Shaw of Greenock and others were encouraged in a proposed
making of salt ‘after a new manner.’ There was a distinct act in
favour of certain other enterprising persons who designed to make
‘salt upon salt.’ John Hamilton, merchant-burgess of Edinburgh, was
endowed with privileges for an invention of his, for mills and engines
to sheel and prepare barley. James Melville of Halhill got a letter of
gift to encourage him in a manufacture of sail-cloth. Inventions for
draining of mines are frequently spoken of.
William Morison of Prestongrange was desirous of setting up a
glass-work at a place within the bounds of his estate, called
Aitchison’s Haven or New Haven, ‘for making of all sorts of glass, as
bottles, vials, drinking, window, mirror, and warck [?] glasses.’ ‘In
order thereto, he conduced with strangers for carrying on the said
work, who find great encouragement for the same, within the said
bounds.’ On his petition, this proposed work, with the workmen and
stock employed, was endowed by the Privy Council (April 27, 1697)
with the privileges accorded to manufactories by acts of parliament.
Connected with Prestongrange in this business was a French
refugee named Leblanc, who had married a Scotchwoman, and got
himself entered as a burgess and guild-brother of Edinburgh,
designing to spend the remainder of his life in the country of his
adoption. It was his part to polish the glass for the making of
mirrors, an art never before practised in Scotland; and this business
he carried on in a workshop in the Canongate. It was found, however,
that ‘the glasses must have mullers and head-pieces of timber, and
sometimes persons of honour and quality desired also tables,
drawers, and stands agreeable to the glass for making up a suit.’
Leblanc offered to employ for this work the wrights of the
corporation of the Canongate; but they plainly acknowledged that
they could not execute it. He was obliged to employ wrights of
Edinburgh. Then came forth the same Canongate wrights, with
complaints of this infraction of their rights. It was a plain case of the
dog in the manger—and the consequence was the stoppage of a
branch of industry of some importance to the community. On
Leblanc’s petition, the Privy Council gave 1696.
him permission to make up the upholstery
work connected with his mirrors, on the simple condition of his
making a first offer of it to the wrights of the Canongate.
One George Sanders had obtained, in 1681, an exclusive privilege,
for seventeen years, for a work for the twisting and throwing all sorts
of raw silk; but he never proceeded with the undertaking. ‘Joseph
Ormiston and William Elliot, merchants,’ proposed (June 1697) to
set up such a work, which they conceived would be useful in giving
employment to the poor, and in opening a profitable trade between
Scotland and Turkey; also in ‘advancing the manufactories of
buttons, galloons, silk stockings, and the like.’ They designed ‘to
bring down several families who make broad silks, gold and silver
thread, &c.,’ and entertained ‘no doubt that many of the Norwich
weavers may be encouraged to come and establish in this country,
where they may live and work, at easy rates.’ On their petition, the
adventurers had their proposed work invested by the Privy Council
with the privileges and immunities of a manufactory.
On the 22d February 1698, David Lord Elcho, for himself and
copartners, besought the favour of the Council for a glass-work
which they proposed to erect at Wemyss. They were to bring in
strangers expert in the art, and did not doubt that they would also
afford considerable employment to natives and to shipping; besides
which, they would cause money to be kept at home, and some to
come in from abroad. They asked no monopoly or ‘the exclusion of
any others from doing their best, and setting up in any other part of
the kingdom they please;’ all they craved was a participation in the
privileges held out by the acts of parliament. Their petition was
cordially granted.
Viscount Tarbat and Sir George Campbell of Cessnock, ‘being
resolved to enter into a society for shot-casting, whereby not only the
exportation of money for foreign shot will be restrained, but also the
product of our own kingdom considerably improved,’ petitioned
(February 1698) for and obtained for the said society all the
privileges accorded by statute to a manufactory for nineteen years.
It was well known, said a petition in September 1698, ‘how much
the burgh of Aberdeen and inhabitants thereof had in all times been
disposed to the making of cloth and stuffs, stockings, plaids, and all
other profitable work in wool.’ It therefore appeared reasonable to
certain persons of that burgh—Thomas Mitchell, John Allardyce,
Alexander Forbes, John Johnstone, and 1696.
others—that a woollen manufactory should
be set up there, and they petitioned the Privy Council for permission
to do so, and to have the usual privileges offered by the statute;
which were granted.[189]
In 1703, a cloth manufactory was in full operation at Gordon’s
Mills, near Aberdeen, under the care of Mr William Black, advocate.
Though established but a year ago, it already produced broad cloths,
druggets, and stuffs of all sorts, ‘perhaps as good in their kind as any
that have been wrought in this kingdom.’ Mr Black had French
workmen for the whitening and scouring of his cloths, and boasted
that he had created a new trade in supplying the country people with
sorted fleece-wool, ‘which is a great improvement in itself.’ Amongst
his products were ‘half-silk serges, damasks, and plush made of wool,
which looks near as fine as that made of hair.’ Unlike most
enterprisers in that age, he desired to breed up young people who
might afterwards set up factories of the same kind, ‘which,’ he said,
‘will be the only way to bring our Scots manufactories to reasonable
prices.’ But he did not propose to do this upon wholly disinterested
principles. He petitioned parliament to make a charge upon the
county of Aberdeen, for the support of boys working at his
manufactory, during the first five years of their apprenticeships;[190]
and his desire was in a modified manner complied with.
About the same time, William Hog of Harcarse had a cloth
manufactory at his place in Berwickshire, where he ‘did make, dress,
and lit as much red cloth as did furnish all the Earl of Hyndford’s
regiment of dragoons with red cloaths this last year, and that in a
very short space.’[191]
It would appear that up to 1703 there was no such thing in
Scotland as a work for making earthenware; a want which, of course,
occasioned ‘the yearly export of large sums of money out of the
kingdom,’ besides causing all articles of that kind to be sold at
‘double charges of what they cost abroad.’ William Montgomery of
Macbie-hill, and George Linn, merchant in Edinburgh, now made
arrangements for setting up ‘a Pot-house and all conveniences for
making of laim, purslane, and earthenware,’ and for bringing home
from foreign countries the men required for such a work. As
necessary for their encouragement in this undertaking, the
parliament gave them an exclusive right of 1696.
making laim, purslane, and earthenware for
fifteen years.[192]
Dec 1.
On a low sandy plain near the mouth of
the Eden, in Fife, in sight of the antique towers of St Andrews, stands
the house of Earlshall, now falling into decay, but in the seventeenth
century the seat of a knightly family of Bruces, one of whom has a
black reputation as a persecutor, having been captain of one of
Claverhouse’s companies. The hall in the upper part of the mansion
—a fine room with a curved ceiling, bearing pictures of the virtues
and other abstractions, with scores of heraldic shields—testifies to
the dignity of this family, as well as their taste. Some months before
this date, Andrew Bruce of Earlshall had granted to his son
Alexander a disposition to the corns and fodder of the estate, as also
to those of the ‘broad lands of Leuchars;’ and Alexander had entered
into a bargain for the sale of the produce to John Lundin, younger of
Baldastard, for the use of the army. Against this arrangement there
was a resisting party in the person of Sir David Arnot of that Ilk.
Sir David, on the day noted, came with a suitable train to Earlshall,
and there, with many violent speeches, proceeded to possess himself
of the keys of the barns and stables; caused the corns to be thrashed;
brought his own oxen to eat part of the straw; and finally forced
Earlshall’s tenants to carry off the whole grain to Pitlethie. The
produce thus disposed of is described as follows: ‘The Mains [home-
farm] of Earlshall paid, and which was in the corn-yard at the time,
six chalders victual, corn, and fodder, estimat this year [1697] at
fourteen pounds the boll, is ane thousand three hundred and forty-
four pounds Scots; and nine chalders of teind out of the lands of
Leuchars-Bruce, corn and fodder, estimat at the foresaid price to two
thousand and sixteen pounds.’
The Privy Council took up this case of ‘high and manifest
oppression and bangstrie,’ examined witnesses on both sides, and
then remitted the matter to the Court of Session.
A similar case of violently disputed rights occurred about the same
time. John Leas had a tack from the Laird of Brux in Aberdeenshire,
for a piece of land called Croshlachie, and finding it a prosperous
undertaking, he was ‘invyed’ in it by Mr Robert Irving, minister of
Towie. The minister frequently threatened 1696.
Leas to cause the laird dispossess him of his
holding, possibly expecting to harass him out of it. Leas stood his
ground against such threats; but, being simple, he was induced to let
Mr Irving have a sight of his ‘assedation,’ which the minister no
sooner got into his hands, than he tore it in pieces. A few weeks after,
May 8, 1693, Irving came to Croshlachie, and causing men to divide
the farm, took possession of one part, put his cattle upon it, and
pulled down two houses belonging to Leas, who was thus well-nigh
ruined.
Still unsatisfied with what he had gained, Irving came, in March
1694, with Roderick Forbes, younger of Brux, whom he had brought
over to his views, and made a personal attack upon Leas, as he was
innocently sowing his diminished acres. ‘Tying his hands behind his
back, [Irving] brought him off the ground, and carried him prisoner
like a malefactor to his house.’ While they were there preparing
papers which they were to force him to subscribe, Leas ‘did
endeavour to shake his hands lowse of their bonds; but Mr Robert
Irving came and ordered the cords to be more severely drawn, which
accordingly was done.’ He was detained in that condition ‘till he was
almost dead,’ and so was compelled to sign a renunciation of his
tack, and also a disposition of the seed he had sown.
On a complaint from Leas coming before the Privy Council, Irving
and young Brux did not appear; for which reason they were
denounced rebels. Afterwards (June 16, 1698), they came forward
with a petition for a suspension of the decreet, alleging that they had
come to the court, but were prevented from appearing by accident. ‘It
was the petitioners’ misfortune,’ they said, ‘that the time of the said
calling they were gone down to the close, and the macers not having
called over the window, or they not having heard, Maister Leas
himself craved [that] the letters might be found orderly proceeded.’
On this petition, the decreet was suspended.
In August 1697, we are regaled with an example of female
‘bangstrie’ in an elevated grade of society. It was represented to the
Privy Council that the wife of Lumsden of Innergellie, in Fife—we
may presume, under some supposed legal claim—came at midnight
of the 22d July, with John and Agnes Harper, and a few other
persons, to the house of Ellieston, in Linlithgowshire—ostensibly the
property of the Earl of Rutherglen—which was fast locked; and there,
having brought ladders with them, they scaled the house, and
violently broke open the windows, at which they entered; after which
they broke open the doors. Having thus 1696.
taken forcible possession of the mansion, they brought cattle, which
they turned loose, to eat whatever fodder the place afforded.
On the petition of the Earl of Rutherglen, this affair came before
the Council, when, the accused lady not appearing, the Lords gave
orders that she and her servants should be cast out of the house of
Ellieston, and that John and Agnes Harper should pay a hundred
pounds Scots as damages, and to be confined (if caught) until that
sum was paid.[193]
Jean Douglas, styled Lady Glenbucket, as 1697.
being the widow of the late Gordon of
Glenbucket, had been endowed by her husband, in terms of her
marriage-contract, with a thousand pounds Scots of free rent out of
the best of his lands ‘nearest adjacent to the house.’ At his death in
1693, she ‘entered on the possession of the mains and house of
Glenbucket, and uplifted some of the rents, out of which she did
aliment her eight children till May [1696],’ when an unhappy
interruption took place in consequence of a dispute with her eldest
son about their respective rights.
According to the complaint afterwards presented by the lady—
though it seems scarce credible—‘she was coming south to take
advice regarding her affairs, when her son, Adam Gordon, followed
her with an armed force, and, on her refusal to comply with his
request that she would return, avowed his determination to have her
back, though he should drag her at a horse’s tail. Then seizing her
with violence, he forced her to return to Glenbucket, three miles, and
immured her there as a prisoner for thirty days, without attendance
or proper aliment; indeed, she could have hardly eaten anything that
was offered for fear of poison; and ‘if it had not been for the charity
of neighbours, who in some part supplied her necessity, she must
undoubtedly have starved.’ The young man meanwhile possessed
himself of everything in the house, including the legal writings of her
property; he left her and her children no means of subsistence, ‘yea,
not so much as her wearing clothes,’ and she ‘was glad to escape with
her life.’ He also proceeded to uplift her rents.
The lady craved redress from the Privy Council, which seems to
have become satisfied of the truth of her 1697.
complaint; but what steps they took in the
case does not appear.[194]
Every now and then, amidst the mingled 1696. Dec. 12.
harmonies and discords proceeding from
the orchestra of the national life, we hear the deep diapason of the
voice of the church, proclaiming universal hopeless wickedness, and
threatening divine judgments. At this time, a solemn fast was
appointed to be held on the 21st of January next, to deprecate ‘the
wrath of God,’ which is ‘very visible against the land, in the
judgments of great sickness and mortality in most parts of the
kingdom, as also of growing dearth and famine threatened, with the
imminent hazard of ane invasion from our cruel and bloody enemies
abroad; all the just deservings and effects of our continuing and
abounding sins, and of our great security and impenitency under
them.’
It was while the public mind was excited Dec. 23.
by the complicated evils of famine and
threatened invasion, that an importation of atheistical books was
found to have been made into Edinburgh, and several young men
were denounced to the authorities as having become infected with
heterodox opinions. At a time when every public evil was attributed
to direct judgment for sins, we may in some faint degree imagine
how even an incipient tendency to irreligion would be looked upon
by the more serious-minded people, including the clergy, and how
just and laudable it would appear to take strong measures for the
repression of such wickedness. We have to remember, too, the
temper of Sir James Steuart, the present public prosecutor. One
delinquent—John Fraser—had, upon timely confession and
penitence, been lightly dealt with; but there was another youthful
offender, who, meeting accusation in a different frame of mind, at
least at first, was to have a different fate.
Thomas Aikenhead, a youth of eighteen, ‘son to the deceest James
Aikenhead, chirurgeon in Edinburgh,’ was now tried by the High
Court of Justiciary for breach of the 21st act of the first parliament of
Charles II., ‘against the crime of blasphemy,’ which act had been
ratified by the 11th act of the fifth session of the parliament of the
present reign. It was alleged in the indictment that the young man
had, for a twelvemonth past, been accustomed to speak of theology
as ‘a rhapsody of feigned and ill-invented nonsense,’ calling the Old
Testament Ezra’s fables, and the New the 1696.
history of the Impostor Christ, further
‘cursing Moses, Ezra, and Jesus, and all men of that sort.’ ‘Likeas,’
pursued this document, ‘you reject the mystery of the blessed Trinity,
and say it is not worth any man’s refutation, and you also scoff at the
mystery of the incarnation of Jesus Christ ... as to the doctrine of
redemption by Jesus, you say it is a proud and presumptuous
device ... you also deny spirits ... and you have maintained that God,
the world, and nature, are but one thing, and that the world was from
eternity.... You have said that you hoped to see Christianity greatly
weakened, and that you are confident it will in a short time be utterly
extirpat.’
Aikenhead, though impenitent at first, no sooner received this
indictment in prison, than he endeavoured to stop proceedings by
addressing to the Lords of Justiciary a ‘petition and retraction,’ in
which he professed the utmost abhorrence of the expressions
attributed to him, saying he trembled even to repeat them to himself,
and further avowing his firm faith in the gospel, in the immortality of
the soul, in the doctrine of the Trinity, and in the divine authority of
Scripture. He alleged, like Fraser, that the objectionable expressions
had only been repeated by him, as sentiments of certain atheistical
writers whose works had been put into his hands by a person now
cited as a witness against him, and ‘who constantly made it his work
to interrogate me anent my reading of the said atheistical principles
and arguments.’ ‘May it therefore please your Lordships,’ said the
petitioner in conclusion, ‘to have compassion on my young and
tender years (not being yet major), and that I have been so
innocently betrayed and induced to the reading of such atheistical
books ... that I do truly own the Protestant religion ... and am
resolved, by the assistance of Almighty God, to make my abhorrence
of what is contained in the libel appear to the world in my
subsequent life and conversation ... to desert the diet against me.’
This appeal, however, was in vain.
The case was conducted by Sir James Steuart, the king’s advocate,
and Sir Patrick Hume, the king’s solicitor.
The witnesses were three students, and a ‘writer,’ all of them about
twenty years of age, being the companions of the culprit, and one of
them (named Mungo Craig) known to be the person who had lent
Aikenhead the books from which he derived the expressions charged
in the indictment. It was proved by the ample depositions of these
young men, that Aikenhead had been accustomed to speak
opprobriously of the Scriptures and their 1696.
authors, as well as of the doctrines of
Christianity; by Mungo Craig alone it was averred that he had cursed

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Haloalkyne Chemistry 1st Edition

Sulfur Chemistry 1st Edition Jiang Xuefeng (Ed.)

A New Paradigm for Environmental Chemistry and

Fair Development in China 1st Edition Qingyun Jiang

Bioactive Materials for Bone Regeneration 1st Edition

New Techniques for Studying Biomembranes 1st Edition

Social Manufacturing: Fundamentals and Applications

Mobile Data Mining and Applications Hao Jiang

China Trade Foreign Direct Investment and Development

Green Chemistry for Sustainability

ISSN 2191-5407 ISSN 2191-5415 (electronic)

Library of Congress Control Number: 2015955865

Springer Heidelberg New York Dordrecht London

Printed on acid-free paper

Springer-Verlag GmbH Berlin Heidelberg is part of Springer Science+Business Media

I am especially grateful to the cooperative contributions made by all the authors.

Guangzhou, China Huanfeng Jiang

Abstract Inspired by the demand of green and sustainable chemistry, modern

© The Author(s) 2016 1

Compound 1 in δ(A) δ(B) δ(C)

Terminal Alkynes Aryl Halide

D R and X Gevorgyan Type III X

Scheme 1.1 Potential reaction pathways of haloalkynes in transition metal catalysis

Abstract Traditionally, haloalkynes were accessible through the deprotonation of

Keywords Terminal alkynes

Haloalkynes were traditionally accessible through the deprotonation of the corre-

© The Author(s) 2016 5

R n-C4H9Li 1) EtMgBr R TMS

Scheme 2.1 Preparation methods for haloalkynes

Scheme 2.2 Representative haloalkynes

Keywords Haloakyne reagents

3.1 Transformations of Carbon-Halo Bond Motif

© The Author(s) 2016 9

Carbon-Halo Bond and

path A path B path C

Scheme 3.1 Reactive sites of haloalkynes

3.1.1 Construction of Carbon-Carbon Bond

3.1.1.1 Construction of C(sp)–C(sp) Bond

Conjugated diynes, especially 1,3-diyne compounds, are of vital signiﬁcance as

Due to the importance of symmetrical 1,3-diyne compounds, they are usually

Scheme 3.2 Pd-catalyzed homo-coupling reactions of iodoalkynes

Scheme 3.3 KI-mediated homo-coupling reactions of haloalkynes

Compared to symmetrical 1,3-diyne compounds, the synthesis of unsymmetrical

Table 3.1 Cu-catalyzed cross-coupling reactions of bromoalkynols

85% 87% 83%

Scheme 3.4 CuFe2O4 nanoparticle catalyzed cross-coupling reactions of haloalkynes

Pd(dba)2 (4 mol%)/L (4 mol%)

Scheme 3.5 Ligand accelerated Pd-catalyzed cross-coupling reactions of bromoalkynes

alkynelboronic acid (1.5 mmol), Cs2CO3 (2 mmol), and CuFe2O4 (5 mol%) in

General Procedure for Ligand Accelerated Pd-Catalyzed Cross-Coupling

Pd(OAc)2 (0.01 mol%)

52% 59% 85%

Scheme 3.6 TBAB stabilized Pd-catalyzed cross-coupling reactions of bromoalkynes

3.1.1.2 Construction of C(sp)–C(sp2) Bond

In 1985, Suzuki and co-workers reported the synthesis of alkyenynes via

Scheme 3.7 Cross-coupling reaction of 1-alkenylboranes with bromoalkynes

conﬁgurations of both the starting alkynylboranes and bromoalkynes were retained.

Scheme 3.8 Development of

[M] or [TM] [M] or [TM]

Scheme 3.9 Pd-catalyzed alkynylation of N-fused heterocycles

of Pd catalyst. The alkynylpalladium intermediate 4, which is essential for con-

CuBr.SMe2 (15 mol%)

26% 84% 71%