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Reactions of metallocarbenes derived

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from N-sulfonyl-1,2,3-triazoles
Cite this: Chem. Soc. Rev., 2014,
43, 5151
Huw M. L. Davies* and Joshua S. Alford

Received 8th February 2014
DOI: 10.1039/c4cs00072b
www.rsc.org/csr
Metal-stabilized carbenes derived from diazo compounds have become broadly useful reactive intermediates
for organic synthesis. This tutorial review will describe the recent advances in using N-sulfonyl-1,2,3-triazoles
as precursors for the formation of metal-bound imino carbene intermediates. These intermediates
undergo a variety of synthetically useful transformations, which include transannulation reactions to
generate new heterocycles, cyclopropanation and subsequent ring expansions, ylide formation with
subsequent rearrangements, and C–H functionalization. Furthermore, many of these transformations
can be conducted with high levels of enantioselectivity by use of chiral rhodium(II) catalysts.

Key learning points

(1) N-Sulfonyl triazoles have emerged as alternative precursors for the formation of metal-bound donor/acceptor carbenes.
(2) The metal-bound imino carbene undergoes many synthetically useful transformations (i.e. cycloadditions, ring expansions, ylide formation, direct
heterocycle synthesis).
(3) N-Sulfonyl triazoles are easily accessed through the copper-catalyzed azide–alkyne cycloaddition reaction.
(4) The formation and reactions of N-sulfonyl triazoles can be performed in a one-pot manner.
(5) The imino carbenes derived from N-sulfonyl triazoles are capable of undergoing a variety of new types of reactions not previously seen with the conventional
ketocarbenes.

1 Introduction
The quest for the discovery of new and powerful synthetic
methods has been at the forefront of organic chemistry research
for more than a century.1 These synthetic methods can connect
readily accessible building blocks and become enabling technol-
ogies with broad impact beyond the field of organic chemistry.
The subject of this review, reactions of metallocarbenes derived
from N-sulfonyl triazoles has generated considerable recent inter-
est in the synthetic community.2 The key reaction sequence,
illustrated in Scheme 1, is the ring opening of triazoles 1 to
generate diazo imines 2 and their subsequent conversion to
metal-bound imino carbenes 3, which then undergo a wide range
of synthetically useful transformations. A previous review in 2011
described the early development of metal-catalyzed reactions of
N-sulfonyl triazoles and pyridotriazoles, with a particular emphasis
on their conversion to different types of heterocycles by means of
transannular reactions.3 Since then, the use of N-sulfonyl triazoles
as metallocarbene precursors has rapidly expanded. The scope of
these new advances will be highlighted in this review.
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA 30322,
USA. E-mail: hmdavie@emory.edu
Scheme 1 Formation of metal-bound imino carbene.
The metal-catalyzed decomposition of diazo compounds
to generate transient metallocarbenes has been exploited in a
variety of useful synthetic transformations.4 The reactivity
profile of metallocarbenes is dependent on the metallocarbene
structure. In recent years, this has led to the classification of
these metallocarbenes according to the substituents adorning
the carbene. Thus, transient metallocarbenes can be divided
into three major groups: acceptor 4, acceptor/acceptor 5, and
donor/acceptor 6, as illustrated in Fig. 1.5 The first two groups,
acceptor- and acceptor/acceptor-substituted carbenes, are highly
reactive species as the electron-withdrawing substituents (EWG;
acceptor groups) flank the electrophilic metallocarbene center.
In general, donor/acceptor-substituted carbenes are more
chemoselective than carbenes that are substituted with only
acceptor groups because the donor group (EDG) modulates the
reactivity of the metal carbene. Consequently, a wide array of

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Fig. 1 The three classes of transient metal carbenes.

recent synthetic advances in this area have been achieved using

donor/acceptor carbenes.3 The N-sulfonyltriazoles 1 offer an entry
to new types of metal-stabilized donor/acceptor and acceptor
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carbenes, which broaden the range of synthetic transforma-

tions available for these useful intermediates.

Scheme 2 Triazole rearrangements/ring-chain isomerization.

2 Historical perspectives
It is well known that 1,2,3-triazoles 7 bearing exocyclic amines
can undergo a rearrangement reaction to isomeric triazoles 10.
The mechanism of the reaction is a ring-opening, ring-closure
sequence, known as the Dimroth rearrangement, which proceeds
by means of imino diazo intermediates, 8 and 9 (Scheme 2).6
1,2,3-Triazoles bearing a strongly electron-withdrawing group at
the N-1 position tend to drive the equilibrium towards the ring-
opened imino diazo structure. In 1967, Hermes and Marsh
reported that at slightly above room temperature, 1-cyano-1,2,3-
triazole 11 exists as a 1 : 1 isomeric mixture of its closed and open-
Scheme 3 Discovery of the rhodium(II)-stabilized imino carbene.
isomer 12.7 Shortly after this report, Harmon and co-workers
found that N-sulfonyl-1,2,3-triazoles 13 with an amino group at
the C-5 position also existed as an isomeric mixture of open (14) serving as an alternative entry into rhodium(II)-stabilized carbenes
and closed-chain (13) isomers.8 (Scheme 3).9 Continued investigation by Gevorgyan in this area,
Recently it was demonstrated that the open-chain diazo com- in collaboration with Fokin, led to the discovery of N-sulfonyl-
pounds from N-sulfonyl-1,2,3-triazoles could be used for the genera- 1,2,3-triazoles 18 as convenient precursors to rhodium(II)-
tion of metallocarbene intermediates. In 2007, Chuprakov and stabilized imino carbenes 19.10 This review will highlight the
Gevorgyan reported that the related 7-chloro-substituted pyridotria- recent development of N-sulfonyl-1,2,3-triazoles as convenient
zole 15 could be effectively decomposed in the presence of a imino carbene precursors and serve as a useful guide for the
rhodium(II) catalyst to reveal a transient rhodium carbene 16, thus development of new reactions of these reactive intermediates.

Huw M. L. Davies was born in Joshua S. Alford graduated with a

Aberystwyth, Wales, UK. He began
his independent academic career
at Wake Forest University. In 1995
he moved to the University at
Buffalo, the State University of
New York, where he held the
positions of UB Distinguished
Professor and Larkin Professor of
Organic Chemistry. In 2008, he
joined the faculty at Emory
University as the Asa Griggs
Huw M. L. Davies Candler Professor of Chemistry.
His research program covers
design of chiral catalysts, development of new synthetic
methodology, total synthesis of biologically active natural
products, and development of chiral therapeutic agents. A major
current research theme in his group is catalytic asymmetric C–H
functionalization. He is the Director of the National Science Founda-
tion Center on Selective C–H Functionalization.
MS degree from Missouri State
University in 2008, under the
mentorship of Dr Chad
Stearman. He started his PhD
studies in 2009 under the
supervision of Prof. Huw M. L.
Davies at Emory University. His
research interests include the use
of N-sulfonyl triazoles for
heterocycle synthesis, expanding
the scope of donor/acceptor
Joshua S. Alford metallocarbenes, and the
synthesis of novel therapeutic
agents for drug abuse.

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3 Synthesis of N-sulfonyl-1,2,3-
triazoles
Triazoles can be easily synthesized by the copper-catalyzed Scheme 5 Synthesis of 4,5-disubstituted N-sulfonyl triazoles.
azide–alkyne cycloaddition reaction (CuAAC) and many reviews
have been published on this topic.11 This reaction allows for
reliable and efficient preparation of 1,4-disubstituted-1,2,3- can be trapped with various electrophiles to form regioselectively
triazoles from terminal alkynes and organic azides with excel- 4,5-disubstituted N-sulfonyl triazoles 21.
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lent selectivity. However, the outcome of the CuAAC reaction

with sulfonyl azides and terminal alkynes in efforts to prepare
1-sulfonyl triazoles is influenced by a variety of factors and
4 Reactions of N-sulfonyl-1,2,3-
requires a judicious choice of reaction conditions. The electron triazoles
deficient sulfonyl azides participate in a number of reactions
N-Sulfonyl triazoles can be effectively decomposed in the presence
with terminal alkynes under the CuAAC conditions giving rise
of a suitable metal catalyst. The resulting a-imino metallocarbenes
to products other than the desired N-sulfonyl-1,2,3-triazole,
are highly electrophilic and undergo a variety of useful transforma-
presumably through an N-sulfonyl ketenimine intermediate
tions, furnishing unique products that are not accessible via
pathway.12 Many groups have exploited the chemistry of the
conventional donor/acceptor a-oxo metallocarbenes. To date, only
N-sulfonyl ketenimine intermediates but this topic is beyond
Ni(cod)2/ligand, Ag(CO2CF3), and Rh2(CO2R)4 have been shown
the scope of this review.
to catalyze this reaction, and of these catalysts rhodium(II)
Traditionally, N-sulfonyl triazoles were synthesized by treat-
tetracarboxylates have proven to be the most versatile.3 It has
ment of the free NH-triazole with a sulfonyl chloride in the
been proposed that the Lewis acidic rhodium(II) catalyst plays
presence of an amine base. The sulfonylation of NH-triazoles
two roles, facilitating the ring-chain isomerization of the triazole
can lead to a mixture of isomeric N2- and N1-sulfonylated
and the subsequent diazo decomposition.10 Many achiral and
triazoles. This is not an efficient procedure for making pre-
chiral rhodium(II) catalysts have been employed. Fig. 2 illustrates
cursors to donor/acceptor metallocarbenes because only the
the most common catalysts used so far. Their specific applica-
N1 isomer can undergo ring-chain isomerization to form the
tion is discussed in more detail later in the text.
desired diazoimine intermediate.
In 2007, Fokin, Chang and Sharpless reported the develop- Synthesis of N-heterocycles
ment of a copper iodide-catalyzed preparation of N-sulfonyl
A distinctive feature of using N-sulfonyl triazoles is the genera-
triazoles 1.13 They found they could regioselectively prepare
tion of metallocarbenes with a pendant sulfonyl imine group.
N-sulfonyl triazoles from a range of terminal alkynes and
The nitrogen atom exhibits a higher nucleophilicity than the
various sulfonyl azides (Scheme 4, condition A). In 2010, Fokin
oxygen atom in the related a-oxo metallocarbene.17 Due to this
reported an improved method for the synthesis of sulfonyl triazoles
increased nucleophilicity, the a-imino group has the ability to
1 from in situ generated CuI-acetylides and sulfonyl azides,14 using
participate in reactions involving zwitterionic intermediates 22,
copper(I) thiophen-2-carboxylate (CuTC) as catalyst (Scheme 4,
which can then cyclize to new heterocycles (Scheme 6).
condition B). Hu, Wang, and co-workers reported an alternative
In 2008, Fokin and Gevorgyan reported that on warming
copper(I)-catalytic system for the synthesis of N-sulfonyl triazoles
N-sulfonyl triazoles 1 in the presence of a rhodium(II) catalyst,
1 in 2011.15 The combination of Cu(OAc)2
H2O–2-aminophenol
they reacted with nitriles in a transannular fashion to furnish
in the presence of terminal alkynes and sulfonyl azides effec-
imidazoles 23 (Scheme 7, top).10 The reaction scope was broad
tively afforded the N-sulfonyl triazoles within minutes in excel-
as various nitriles and N-sulfonyl triazoles participated in
lent yields with high selectivity (Scheme 4, condition C). Notably,
electron deficient alkynes still participated in the reaction albeit
in lower yields.
Recently, Croatt reported a selective synthesis of 4,5-disub-
stituted N-sulfonyl triazoles 21 (Scheme 5).16 The treatment of
terminal alkynes under strongly basic conditions in the
presence of sulfonyl azides results in the selective formation
of 5-substituted N-sulfonyl triazoles in which the triazole anion

Scheme 4 Synthesis of 4-substituted N-sulfonyl-1,2,3-triazoles. Fig. 2 Rhodium(II) tetracarboxylate catalysts.

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Scheme 6 Formation of the zwitterionic intermediates.

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Scheme 8 Davies’ synthesis of trisubstituted pyrroles.

involves the furans 26 reacting with the electrophilic rhodium(II)-

stabilized metallocarbenes at the C-3 position to generate zwitter-
ions 27, which then close to the hemiaminals 28. Under the
mildly acidic reaction conditions, the ring then opens to 29,
which then aromatize to the pyrroles 30.
Scheme 7 Early reports of heterocycle synthesis with N-sulfonyl triazoles.
Expanding on this reaction, Davies reported a rhodium(II)-
catalyzed synthesis of pyrroloindolines 35 via an enantioselective
the reaction. Shortly after this, Murakami reported a nickel/ formal [3+2] cycloaddition between 4-aryl sulfonyltriazoles 1 and
aluminum-catalyzed denitrogenative transannulation of N-sulfonyl C-3 substituted indoles 31 (Scheme 9).21 The reaction proved to
triazoles with internal alkynes.18 The combination of a nickel(0) be most effective in both conversion and enantioinduction when
catalyst, Ni(cod)2, electron-rich and bulky phosphine ligand, conducted in nonpolar hydrocarbon solvents with Rh2(S-PTAD)4
P(nBu)Ad2, and a Lewis acid additive, AlPh3, provided an effec- being the optimal catalyst. A variety of electron-withdrawing
tive transannulation of symmetrical internal alkynes furnishing and electron-donating aryl-substituted mesyltriazoles success-
the corresponding substituted pyrroles 24 in moderate yields fully participated in the reaction providing good yields of 35
(Scheme 7, middle). However, the use of unsymmetrical alkynes with high levels of enantioselectivity. The reaction was found to
gave a mixture of regioisomers and terminal alkynes failed to be susceptible to steric effects as substrates with bulky sulfonyl
participate in the reaction. Gevorgyan then reported the trans-
annulation of N-tosyl triazoles with terminal alkynes using a
dual rhodium/silver catalyst system.19 Various C-4 substituted
triazoles and electron-rich terminal alkynes participated in the
reaction to provide the desired pyrrole products 25 in good yield;
however, electron-poor terminal alkynes did not participate in
the reaction (Scheme 7, bottom). The methodology was extended
into a three-component, one-pot procedure starting from tosyl
azide and two different terminal alkynes, one of which is first
added to form the N-tosyl triazole. These early reports are
thoroughly discussed in an earlier review3 and will not be
considered in further detail here.
In the last few years, a number of new transannulation
reactions have been described. Davies reported a synthesis of
trisubstituted pyrroles 30 from a rhodium(II)-catalyzed transan-
nulation of N-sulfonyl triazoles with 2,5-disubstituted furans 26
(Scheme 8).20 Steric and electronic variations of the triazole had
minimal impact on the efficacy of the reaction, but in some
cases when the furan was unsymmetrically substituted, mix-
tures of regioisomers were formed. Although most of the
rhodium(II) carboxylate catalysts were effective, Rh2(S-DOSP)4
was found to be the optimal catalyst. The proposed mechanism Scheme 9 Davies’ enantioselective synthesis of pyrroloindolines.

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Scheme 10 Fokin’s enantioselective synthesis of 4-oxazolines.
groups or bulky groups at the indolic nitrogen failed to furnish
pyrroloindolines.
Two possible reaction pathways have been proposed for this
transformation.23 In the first pathway (path a), similar to reaction
with furans, the electron-rich indoles react with the electrophilic
rhodium(II)-stabilized imino metallocarbenes 3 via a zwitterionic-
type pathway (intermediates 32), followed by cyclization to
the pyrroloindolines 35. In the second pathway (path b), the
reaction occurs via an initial cyclopropanation of the indoles
(intermediates 33), followed by a subsequent ring opening of
the strained cyclopropylindolines 33 and recombination to furnish
the pyrroloindolines 35. The second pathway is more consistent
with the observed regioselectivity because the direct attack of the
metallocarbenes on the indoles 31, would be expected on steric
grounds to form zwitterions bound at C-2 rather than C-3.
Diazocarbonyl derivatives 36 react with carbonyl groups to
produce either ylides 37 or epoxides 38, depending on the
nature of the R1 group as depicted in Scheme 10. The ylides
37 derived from alkyl diazocarbonyl derivatives can further react via
1,3-dipolar cycloaddition to provide complex structures. Fokin
reported similar ylide formation between Rh(II)-stabilized imino
metallocarbenes and aldehydes 39.22 The reaction proceeds via ylide
intermediates 40, which undergo an intramolecular cyclization with
the pendant sulfonyl imine to provide 3-sulfonyl-4-oxazolines 41 in
excellent yields and high levels of enantioselectivity. A variety of aryl
and alkyl aldehydes 39 participate in the reaction with optimal
outcomes being obtained with the use of 1-mesyl-1,2,3-triazoles 1 at
ambient temperature with the rhodium(II) catalyst, Rh2(S-NTTL)4,
in chloroform. Prolonged reaction times significantly lowered
the enantiomeric purity of the products due to the reversible
ring opening of the N,O-aminal in 41 under the slightly acidic
reaction conditions.
Murakami and Miura have reported an extension of this
reaction to a,b-unsaturated aldehydes 42 furnishing trans-2,3-
disubstituted dihydropyrroles 49 (Scheme 11).17 The reaction
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Scheme 11 Murakami and Miura’s synthesis of trans-2,3-disubstituted
dihydropyrroles.
conditions are similar to that reported by Fokin for the synthesis
of 4-oxazolines with the exception of heating to 120 1C. This
slight change in conditions favours the formation of dihydro-
pyrroles 49. It is proposed that the reaction first produces
4-oxazolines 45 as seen previously, but under the more vigorous
conditions, the weak aminal bond is cleaved producing zwitter-
ionic intermediates 46 followed by a double bond isomerization
to the more stable (E) isomers 47. The enolate moiety of 48
then engages the a,b-unsaturated imine through a conjugate
addition to provide the 2,3-dihydropyrroles 49. Alternatively, a
[3,3] sigmatropic rearrangement of 45 is also possible. A one-pot
procedure for the synthesis of trans-2,3-disubstituted dihydro-
pyrroles was carried out to demonstrate the practicality of the
method starting from the terminal alkyne, in which the triazoles
1 were produced in situ.
In addition to aldehydes, N-sulfonyl triazoles react with
aldimines 50 through a cyclization–elimination sequence, providing
direct access to 1,2,5-trisubstituted imidazoles 53 (Scheme 12).22
The imidazoles are formed in moderate yield (54–90%) from the
corresponding 4-aryl-substituted triazoles and aldimines. The
reaction proceeds through a cyclization of ylide intermediates 51
to provide imidazolines 52, which then eliminate sulfinic acid to
provide imidazoles 53. Fokin has also disclosed an efficient
method for the construction of imidazolones 55 and thiazoles
57 via a Rh(II)-catalyzed formal [3+2] cycloaddition of 1-mesyl-
1,2,3-triazoles with isocyanates 54 and isothiocyanates 56,
respectively.23 The nitrogen of the isocyanates react with
the imino metallocarbenes forming ylide-type intermediates,
followed by cyclization to furnish the imidazolones 55. In the
case of isothiocyanates, the sulfur reacts to form the ylide-type
intermediates, which then cyclize to provide the thiazoles 57
with an exocyclic imine group.
Recently Sarpong demonstrated that a-alkyl imino metallo-
carbenes 59 generated from the rhodium(II)-catalyzed decom-
position of N-sulfonyl triazoles 58 could react with pendant
allene moieties to form 3,4-fused pyrroles 62 (Scheme 13).24 The
initially formed ylides 60, underwent cyclization to dihydro-
pyrroles 61, which isomerized to the pyrroles 62. A variety of
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Scheme 14 Murakami and Miura’s synthesis of pyrroles from allenes.

zwitterionic intermediates 67. Subsequent cyclization of 67

furnishes isopyrroles 68 with release of the nickel catalyst,
Scheme 12 Fokin’s imidazole, imidazolone, and thiazole synthesis. which can undergo double bond transposition in the presence
of an acid to the pyrroles 69.
Davies reported that in the absence of a suitable trapping agent,
4-alkenyl-N-sulfonyl triazoles 70 participate in a rhodium(II)-
catalyzed 4p electrocyclization with the adjacent alkenyl moiety
to furnish 2,3-fused pyrroles 74 in good to excellent yields
(Scheme 15).27 The 4-alkenyl-N-sulfonyl triazoles could be
readily derived from the corresponding ketones allowing for a
highly efficient synthesis of the 2,3-fused pyrroles. The highest
yields were obtained when N-tosyl triazoles and the more robust
rhodium(II) catalyst, Rh2(esp)2, were used. The reaction was further
extended to the synthesis of substituted indoles 76 starting from
cyclic enynes 75 in a one-pot cyclization, aromatization sequence.
Shortly after this, Gevorgyan reported that a-alkyl imino metallo-
carbenes could engage with pendant alkynes via an alkyne–carbene
metathesis step resulting in the synthesis of 3,4-fused pyrroles 81
(Scheme 16).28 Similar to the Davies’ report,27 the rhodium(II)
Scheme 13 Sarpong’s synthesis of 3,4-fused pyrroles.
catalyst, Rh2(esp)2, proved to be particularly effective in this trans-
formation. Mechanistically, it is proposed the pendant alkynes
groups on the allene, including aryl, cycloalkyl, and alkyl, were interacts with the electrophilic imino metallocarbenes 78 in an
tolerated. Notably, the a-alkyl group did not undergo the competing alkyne-metathesis step to form rhodium(II)-stabilized carbenes 79.
1,2-hydride shift to yield a,b-unsaturated N-tosylimines as seen in
the reports of Murakami and Fokin.2,25 This reaction was further
extended to a one-pot sequence starting from allenylalkynes and
resulting in the in situ formation of the triazoles 58 and their
conversion to pyrroles 62. The utility of this reaction was demon-
strated in the enantioselective synthesis of the natural product
cycloprodigiosin 64 in four steps starting from the enantio-
enriched allenylalkyne 63.
Murakami and Miura have reported a nickel(0)-catalyzed
transannulation of N-sulfonyl triazoles 21 with allenes 65 to
furnish isopyrrole intermediates 68, which could be further
elaborated into polysubstituted pyrroles or participate in sub-
sequent Alder–ene reactions with suitable enophiles in situ
(Scheme 14).26 A variety of electron-withdrawing and electron-
donating aryl- and alkyl-substituted N-sulfonyl triazoles successfully
participated in the reaction. Interestingly, both 1,5-disubstituted
and 1,4,5-trisubstituted N-sulfonyl triazoles were also tolerated
in the reaction. A plausible mechanism for this transformation
begins with the formation of the imino nickel carbenes 66
followed by nucleophilic addition of the allenes to yield Scheme 15 Davies’ synthesis of 2,3-fused pyrroles and indoles.

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Scheme 16 Gevorgyan’s synthesis of 3,4-fused pyrroles.
Nucleophilic attack by the sulfonyl imine, followed by aroma-
tization of the zwitterionic intermediates 80 provided the fused
pyrroles. Only substrates with a C-3 tether furnished the desired
pyrrole products but several functional groups were compatible
with this chemistry.
Stereoselective cycloadditions
The metal-catalyzed decomposition of diazo compounds in the
presence of alkenes is a general method for the synthesis of
cyclopropanes.4,29 In particular, rhodium(II)-catalyzed cyclopro-
panation of alkenes with donor/acceptor carbenes has been
shown to be an effective method for the enantioselective
synthesis of cyclopropanes generating one or more quaternary
stereogenic centers. Fokin and co-workers reported two examples
of a highly diastereo- and enantioselective rhodium(II)-catalyzed
cyclopropanation of alkenes 82 with the imino metallocarbenes
derived from N-sulfonyl triazoles 1 (Scheme 17).30,31 Subsequent
hydrolysis of the resulting sulfonyl imines 83 gave quick and ready
access to cyclopropyl carboxaldehydes 84 in good yields and
high enantioselectivity. The reduction of the sulfonyl imines 83
provided N-sulfonyl homoaminocyclopropanes in excellent
yields and high enantioselectivity.30 However, the reaction
proved to be highly dependent on the nature of the sulfonyl
group as the use of tosyl triazole afforded the cyclopropyl
carboxaldehydes 84 in good yield, but low enantioinduction.
Switching the sulfonyl group to the less sterically encumbered
mesyl resulted in an improved reaction with good yield of 84
and very high levels of enantioinduction when Rh2(S-NTTL)4
was used as catalyst.
Fokin went on to further illustrate that the reaction could be
performed starting from the readily accessible NH-triazoles 85,
Scheme 17 Fokin’s enantioselective cyclopropanation.
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Scheme 18 Fokin’s enantioselective cyclopropanation of N–H triazoles.
which could be sulfonylated in situ by triflic anhydride in the
presence of a hindered pyridine base at low temperatures
(Scheme 18).31 Interestingly, the reaction allowed for a visual
readout of the reaction progress: a purple solution resulted
from the complexation of the NH-triazole and the rhodium(II)
catalyst, but turned green upon the addition of triflic anhydride
indicating all of the NH-triazole had been sulfonylated. Reac-
tion with an electron rich olefin, 4-methoxystyrene, leads to the
formation of a 2,3-dihydropyrrole product 86 with moderate
enantioinduction.32 The use of an electron-withdrawing group
at the C-4 position of the triazole also resulted in the forma-
tion of a 2,3-dihydropyrrole product, but as a racemate. It was
concluded that the two products must arise via different reac-
tion pathways.
Murakami and Miura have reported a rhodium(II)-catalyzed
dearomatizing [3+2] annulation of 4-(3-arylpropyl) N-sulfonyl
triazoles 87 to furnish 3,4-fused indoles 90 (Scheme 19).33 The
proposed mechanism involves an intramolecular attack of the
rhodium(II) imino-carbenes 88 by the aryl substituent in a 6-exo
mode providing intermediates 89 followed by cyclization of the
imino group to provide the cis-3,4-fused indoles 90. A variety of
substituted aryl groups possessing the three-carbon tether were
tolerated, but shorter or longer tethers failed to participate in
the reaction. The use of a chiral catalyst, Rh2(S-TCPTTL)4,
provided 3,4-fused indole 92 with a good level of asymmetric
induction (81% ee) in a one-pot sequence starting from the
5-aryl-1-alkyne 91.
Scheme 19 Murakami and Miura’s 3,4-fused indole synthesis.
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Scheme 20 Davies’ enantioselective formal 4+3 cycloaddition.
The rhodium(II)-catalyzed decomposition of alkenyl-substituted
diazoacetates in the presence of dienes results in a formal [4+3]
cycloaddition reaction to yield seven-membered rings, occurring via
a tandem cyclopropanation/Cope rearrangement.34 Davies recently
demonstrated that the alkenyl N-sulfonyl triazoles 70 could also
participate in a tandem cyclopropanation/Cope rearrangement
(Scheme 20).35 Rh2(S-NTTL)4 was the optimal catalyst for inducing
high yields and high levels of enantioselectivity. The reaction
scope revealed that various cyclic and heterocyclic alkenyl-
substituted sulfonyl triazoles 70 were tolerated. This reaction
provides an effective method for the enantioselective synthesis
of polycyclic imines 95 generating two stereogenic centers. The
triazole approach offers considerable benefits over the alkenyl-
diazoacetate approach to the vinylcarbene intermediates because
many alkenyldiazoacetates rapidly decompose by an intramolecular
6p electrocyclization to pyrazoles.36
Recently, Davies reported a stereoselective cyclopropanation
of olefins with 4-phthalimido sulfonyltriazole 96 (Scheme 21).37
This is an important advance because nitrogen-based donor
groups cannot be incorporated into pre-formed diazo com-
pounds. These types of diazo compounds are too unstable to
be isolated. The donor group influences the stability of the
triazole and the imino diazo compound because 96 reacts
thermally at 55 1C without catalyst. A variety of alkenes and
dienes undergo a highly diastereoselective cyclopropanation
leading to a-amino cyclopropylcarboxaldehydes 97 in good to
excellent yields. Furthermore, the reaction can be conducted in
a one-pot procedure starting from the N-ethynylphthalimide.
There are two proposed reaction pathways for the thermal
transformation. In the first pathway, a classic 1,3-dipolar
Scheme 21 Davies’ synthesis of a-amino cyclopropanes.
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Scheme 22 Fokin’s stereoselective arylation.
cycloaddition occurs between the olefin and diazo tautomer to
form a pyrazoline, followed by a thermal dinitrogen extrusion event
to provide the cyclopropyl product. In the second pathway, there is
a thermal decomposition of the diazo tautomer to reveal an imino
carbene that undergoes a direct cyclopropanation with the olefin.
The phthalimido group could be subsequently deprotected,
resulting in a direct entry to cyclopropyl amino acids.
Stereoselective arylation
Fokin has recently reported a direct rhodium(II)-catalyzed aryla-
tion of imino metallocarbenes derived from 1 with boronic
acids 98 to stereoselectively furnish 2,2-diaryl enamines 101 as
depicted in Scheme 22.38 A variety of electron-withdrawing and
electron-donating aryl-substituted sulfonyltriazoles successfully
participated in the reaction providing the corresponding
2,2-diaryl enamines 101 in good yield. During the course of the
study, calcium chloride was found to be an essential additive for the
dehydration of the boronic acid substrate to the arylboroxine trimer,
which is likely the active arylating species in the reaction. The diaryl
enamines 101 can be readily converted to aryl-substituted indoles. It
is proposed that the arylation of the rhodium(II) imino-carbenes
3 begins with a coordination of the sulfonylimine in 3 to the
arylboroxine trimer followed by an irreversible facial-selective
delivery of the aryl group as shown in 99.
Stereoselective 1,1- and formal 1,3-insertions
Rhodium(II)-stabilized carbenes 102 derived from diazoacetates
readily undergo a stereoselective 1,1-insertion reaction with
C–H bonds to form 103 (X = CR3), (Scheme 23). The reaction is
a concerted asynchronous process that is initiated by a hydride
abstraction-like event.6 The reaction can also be extended to O–H
and N–H bonds but 103 X = OR, NR2a are typically formed as a
racemic mixture. The O–H and N–H insertion proceeds via the
formation of an ylide intermediate, followed by a proton
abstraction to form enols, which then tautomerize to the final
products. Similar reactions can be conducted with imino-
carbenes 3 but in the case of O–H and N–H insertions, the
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Scheme 23 Different possible insertion pathways.

Scheme 25 Reaction of N-sulfonyl triazoles with water and alcohols.

imino carbenes into the O–H bond of allylic alcohols generates

a-imino enols 115 followed by a subsequent Claisen-like
Scheme 24 Fokin’s enantioselective C–H insertion.
[3,3]-sigmatropic rearrangement (intermediate 116) to provide
a-allyl-a-amino ketones 117 (Scheme 26). This transformation
allowed for a regioselective functionalization of a terminal
alkyne with the formation of C–O, C–N, and C–C bonds in
enamines 105 are the isolated products because they do not
the same reaction media using sulfonyl azides and allylic
tautomerize to imines.39
alcohols. The reaction tolerated both aryl- and alkyl-acetylene
Recently, Fokin demonstrated that rhodium(II) imino car-
derivatives with allylic alcohol 113 providing the corresponding
benes derived from N-sulfonyl triazoles 1 could undergo an
product in a one-pot manner in moderate to good yields.
enantioselective C–H insertion into unactivated alkanes 106 to
Fokin later found that the O–H insertion reaction could also be
furnish a variety of chiral N-sulfonylamines 107 in good yield
extended to carboxylic acids 118 to provide access to 2-acyloxy-
and high enantioselectivity (Scheme 24).40 This 1,1-insertion
enamines 119 (Scheme 27).39 N-Sulfonyl triazoles 1 underwent an
reaction tolerated both electron-withdrawing and electron-
O–H insertion reaction in a slight excess of a benzoic acid to give
donating aryl groups on the triazole as well as different sulfonyl
119 in excellent yields and exclusively as the Z isomers. However,
groups at the N-1 position. Intriguingly, the imino metallocar-
when a less sterically demanding, or non-aromatic carboxylic
bene has a higher chemoselectivity towards insertion into
acids were employed the direct formation of N-acyl a-amino
tertiary C–H bonds over secondary C–H bonds as compared
ketones 121 was observed in moderate yields. It is presumed
to diazoacetates.41 The change in chemoselectivity towards
the carbonyl group of the initial enamines 120 is attacked by the
tertiary C–H bonds is attributed to the lower steric demand of
nitrogen atom of the enamide in this series.
the sulfonyl imine group compared to the ester group of the
Fokin also found that a formal 1,3-insertion of the rhodium(II)
diazoacetate.
imino carbene into N–H bonds of primary and secondary amides
Murakami reported the regioselective synthesis of a-amino
could be achieved providing diamines in high yield as a single
ketones via rhodium(II)-catalyzed denitrogenative hydration of
regio- and stereoisomer (Z-geometry; Scheme 28).39 Various aryl-
N-sulfonyl triazoles 1 with water (Scheme 25).25 The insertion of
substituted sulfonyl triazoles successfully participated in the
rhodium(II)-stabilized imino carbenes into the O–H bond
of water resulted in the formation of a-imino enols 109
followed by a tautomerization to a-amino ketones 110. Aryl-
and alkenyl-substituted sulfonyl triazoles successfully partici-
pated in the hydration reaction with Rh2(oct)4 but in the case of
alkyl-substituted sulfonyltriazoles, b-hydride migration to form
a,b-unsaturated N-sulfonyl imines was a side reaction. An
analogous reaction was preformed using t-butyl alcohol in
place of water resulting in the formation of a-amino enol ether
112. Fokin and co-workers later followed up this reaction with a
more extended study of the substrate scope with aryl, aliphatic,
and silyl protected alcohols to generate a-imino enols 109.39
The reaction of ketocarbenes with allyl alcohols results in
ylide formation followed by either a [3,3] or [2,3] sigmatropic
rearrangements.42 Murakami reported that the reaction of
N-sulfonyl triazoles with allyl alcohols results in a [3,3] sigma-
tropic rearrangement.43 The insertion of rhodium(II)-stabilized Scheme 26 Murakami’s synthesis of a-allyl-a-amino ketones.

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Scheme 27 Fokin’s O–H insertion with carboxylic acids in which two
reaction pathways are possible.
Scheme 28 Fokin’s N–H insertion of N-sulfonyl triazoles.
reaction leading to the substituted Z-enamides 124 in good
yield. A number of primary carbamates and primary alkyl,
alkenyl, and aryl amides were effective substrates. When the
reaction was extended to secondary amides 125, the selectivity
and efficiency of the reaction (O–H vs. N–H insertion) were
highly dependent on the nature of the amide partner. Less
steric congestion of the N–H bond of the secondary amide
lead to formation of the diamines 126, whereas more steric
congestion about the N–H bond lead predominately to 128
presumably via 127.
Murakami later found that N-sulfonyl triazoles will undergo
a Doyle–Kirmse reaction with an allyl sulfides 129 in the
presence of a rhodium(II) catalyst to furnish a-allyl-a-sulfanyl
imines 131 (Scheme 29).44 The resulting imines 131 can then be
reduced with a hydride source, or hydrolyzed to aldehydes under
acidic conditions for ease of isolation. It is proposed the allyl
sulfides 129 attack the electrophilic metallocarbenes generating
ylide intermediates 130 followed by a [2,3] sigmatropic rearran-
gement to afford a-allyl-a-sulfanyl imines 131. Various aryl- and
alkyl-substituted sulfonyl triazoles successfully participated in
the reaction in moderate yields. The group of Anbarasan recently
reported similar results with allyl sulfides.45
Ring expansion and 1,2 migrations
One of the most common reactions of metallocarbenes derived
from a-alkyl diazocarbonyl compounds is an intramolecular
[1,2] shift.46 Recently it has been shown that alkyl-, cycloalkyl-,
and alkanol-substituted sulfonyl triazoles undergo a similar
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Scheme 29 Murakami’s synthesis of a-allyl-a-sulfanyl imines.
metal-catalyzed ring expansion/rearrangement. Tang et al. first
reported the synthesis of cyclobutenes via a silver-catalyzed ring
expansion of cyclopropyl-substituted sulfonyl triazoles.47 Shortly
after, the groups of Murakami and Fokin greatly expanded on this
reaction.48,49 They both independently reported the rhodium(II)-
catalyzed ring expansion/rearrangement of cycloalkanol- and
alkanol-substituted sulfonyl triazoles 133 giving access to various
enaminones and substituted olefins (Scheme 30). The reaction
involves the migration of the adjacent alkyl groups to the metal-
locarbenes presumably through a tautomerization of the enols
136. The Z-substituted enaminones 137 were formed exclusively
presumably because they are stabilized through intramolecular
hydrogen bonding. Similar to [1,2] migrations of metallocarbenes
derived from a-diazocarbonyl compounds, the migratory aptitude
of 1-triazolyalkanols appears to follow the trend: hydride 4
phenyl 4 primary alkyl 4 secondary alkyl.
Fokin further expanded the rearrangement concept to sulfonyl
triazoles 138 bearing either a tertiary or quaternary center at C-4
to furnish dienes 141 (Scheme 31).50 Cycloalkyl and tert-alkyl
triazoles provided the expected hydride and alkyl shift, respec-
tively, whereas protection of an alcohol as an acetoxy led to the
exclusive migration of the acetoxy group furnishing acetyl enols
in excellent yields. More interestingly, a piperazine triazole led
to a selective migration of the amino group to provide the
corresponding imine enamine in good yield.
Scheme 30 Ring expansion/rearrangement of alkanol-substituted
N-sulfonyl triazoles.
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Scheme 31 1,2-Migration of sulfonyltriazoles bearing a quaternary center
at C-4.
Since the submission of this manuscript, several additional
reactions of N-sulfonyl triazoles have been reported. Boyer
reported the rhodium(II)-catalyzed transformation of 4,5- and
5-substituted N-sulfonyl triazoles bearing allyl and propargylic
ethers into dihydrofuran-3-imines.50 Lee reported an extension of
the formal 3+2 cycloaddition of electron rich olefins to alkenyl
ethers to afforded substituted pyrroles after the elimination of
ethoxide.51 Following up on Fokin’s formal 1,3-insertion chemistry,
Lee reported the synthesis of cis-diamino enones from
N,N-dialkylsubstituted formamides.52 Tang and Shi have reported
the intramolecular annulation of pyrrolyl and indolyl triazoles to
provide azepine derivatives.53 Tang described an alternative entry
into azepines by a tandem cyclopropanation/aza-Cope rearrange-
ment.54 Anbarasan reported the direct arylation of the imino
carbenes to form diarylenamides.55
5 Conclusions
The use of N-sulfonyl-1,2,3-triazoles as precursors for the for-
mation of metal-bound donor/acceptor and acceptor carbenes
has led to a diverse range of products previously inaccessible
from traditional donor/acceptor carbene chemistry derived
from diazoacetates. This field has seen rapid expansion in
the last 2–3 years and led to many novel, stereoselective
transformations, direct heterocycle synthesis, and implementa-
tion of heteroatoms as the donor group, through the use of
these relatively stable a-imino metallocarbenes. The equili-
brium between the open and closed isomers of the triazole
allows for a low concentration of the reactive a-imino diazo
species obviating the need for slow addition. The N-sulfonyl
triazoles are readily available through an experimentally simple
and environmentally friendly copper-catalyzed azide–alkyne
cycloaddition reaction. The reaction tolerates many alkyne
partners and sulfonyl azides allowing for a careful reactivity
tuning of the N-sulfonyl triazoles. Furthermore, many of the
developed reactions can be performed in a one-pot procedure
starting from alkynes and sulfonyl azides thus eliminating an
isolation step. In the future, a more diverse screening of metal
catalysts could further expand the reaction scope of N-sulfonyl-
1,2,3-triazoles and may lead to new reactivity.
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Acknowledgements
We wish to thank the current and past members of the Davies
group who have contributed to our studies of donor/acceptor
carbenes, especially those who contributed to the use of N-sulfonyl
triazoles as carbene precursors. Financial support for much of
the research described in this review was obtained from the
National Science Foundation (CHE 1213246).
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