Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective Hydrocarboxylation of Internal Alkynes

Article abstract of DOI:10.1021/acscatal.5b02090

We report the highly efficient gold-catalyzed hydrocarboxylation of internal alkynes that operates under solvent- and silver-free conditions. This new, simple, and eco-friendly protocol allows for the synthesis of a wide variety of functionalized aryl and

Full text of DOI:10.1021/acscatal.5b02090

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Article
Highly Efficient Gold(I)-Catalyzed Regio- and
Stereoselective Hydrocarboxylation of Internal Alkynes
Stephanie Dupuy, Danila Gasperini, and Steven P. Nolan
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.5b02090 • Publication Date (Web): 12 Oct 2015
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Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective
Hydrocarboxylation of Internal Alkynes.
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Stéphanie Dupuy†, Danila Gasperini† and Steven P. Nolan§*
†EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9 ST, U.K.
§ Chemistry Department, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia).
KEYWORDS gold catalysis, carboxylic acids, internal alkynes, N-heterocyclic carbenes, cooperativity
ABSTRACT: We report the highly efficient goldꢀcatalyzed hydrocarboxylation of internal alkynes that operates under solventꢀ and
silverꢀfree conditions. This new simple and ecoꢀfriendly protocol allows for the synthesis of a wide variety of functionalized aryl
and alkyl enol esters in high yields, with Zꢀstereospecificity, good regioselectivities and without the requirement for purification by
chromatography. This process represents an expedient, operationally simple method for the synthesis of enol esters.
Enol esters are highly versatile building blocks in organic
synthesis.1 They are widely used industrially in polymerization
processes2 and have also been shown to be valuable reagents
in a variety of synthetic transformations.3 Among a wide vaꢀ
riety of synthetic approaches previously developed, the direct
addition of widely available and inexpensive carboxylic acids
starting materials to alkynes represents the most efficient route
to access vinyl esters due to excellent atomꢀ and stepꢀ
economies.4 While the intermolecular addition of carboxylic
acids to terminal alkynes has been extensively studied,5 the
use of unactivated internal alkynes has been shown to be parꢀ
ticularly difficult and requires high catalyst loadings, long
reaction times and increased temperatures.6 Additionally,
further challenges remain in developing the next generation of
such reactions, namely the regioꢀ, stereoꢀ and chemoselectivity
(Markovnikov and antiꢀMarkovnikov products) of these reacꢀ
tions. Furthermore achieving this in a manner where products
can be accessed efficiently, with minimal waste and purificaꢀ
tion would be quite an achievement. There is a clear need for
new methods to overcome these challenges and limitations.
smoothly using low loadings of [Au] but required long reacꢀ
tion times (12ꢀ24 h).
To the best of our knowledge, no report of a highly efficient
and broadly applicable hydrocarboxylation of internal alkynes
using gold and especially (NHC)Au catalyst systems has been
disclosed to date. Our group recently demonstrated that
[{Au(IPr)}2(µꢀOH)][BF4] (1a) is a highly efficient bifuncꢀ
tional catalyst for the hydrophenoxylation of internal alkynes.9
Notably, this complex can be regarded as a dualꢀmode activatꢀ
ing catalyst providing Lewis acid [Au(IPr)][BF4] (1b) and
Brønsted base [Au(IPr)(OH)] (1c) fragments (eq. 1).9b
(1)
[Au(IPr)][BF4]
+
[Au(IPr)(OH)]
[{Au(IPr)}2(ꢀ-OH)][BF4]
1a
1b
1c
Lewis acid
Brønsted base
We envisioned that this strategy could also be applied sucꢀ
cessfully to accomplish other challenging reactions such as the
intermolecular addition of carboxylic acids to internal alkynes
to produce a broad variety of functionalized enol esters with
hopefully excellent regioꢀ and stereoselectivity.
With its high affinity for πꢀsystems, gold has been shown to
be uniquely effective in the addition of nucleophiles to unsatuꢀ
rated systems such as alkynes or allenes.7 While numerous
reports describe the cyclization of alkynoic acids to give γꢀ
lactones,8 examples of the intermolecular addition of carboxꢀ
ylic acids to alkynes catalyzed by gold remain few. So far,
only two reports using Au(I) can be found in the literature. In
2010, Chary et al. reported the hydrocarboxylation of alkynes
using 5 mol% of [Au(PPh3)Cl]/AgPF6.5j This methodology
was applied to various terminal alkynes but was only demonꢀ
strated with four internal alkynes. In particular, incomplete
conversion and lower yield were observed when using unreacꢀ
tive diarylꢀsubstituted alkynes. A recent report by Zhang and
coꢀworkers described a strategy using a tailored phosphine
ligand to direct and promote the nucleophilic addition to goldꢀ
activated alkynes.5k The addition of benzoic acid to three
internal aliphatic alkynes was examined and proceeded
Initially, diphenylacetylene (2a) and the sterically hindered
2,6ꢀdimethoxybenzoic acid (3a) were selected as model subꢀ
strates. To our delight, the addition of 3a to 2a (1.1. equiv.), at
85 °C in technicalꢀgrade toluene (1M) in the presence of 2
mol% of [{Au(IPr)}2(µꢀOH)][BF4] 1a gave complete converꢀ
sion to vinyl ester (4aa) as a single stereoisomer, after 16 h
1
(Table 1, entry 1). The H NMR of the reaction mixture conꢀ
firmed the stereospecific formation of (Z)ꢀisomer. Subsequentꢀ
ly, various gold catalysts were examined. Interestingly, the
Brønsted base [Au(IPr)(OH)] 1c gave only 40% conversion
while cationic Gagosz complex [Au(IPr)(NTf2)]10 1f alone
failed to catalyze the hydrocarboxylation of 2a (Table 1, enꢀ
tries 3ꢀ4). High conversion was obtained using
[Au(IPr)(MeCN)][BF4] 1e catalyst, albeit longer reaction time
was required and the desired vinyl ester was formed along
with 15% of ketone sideꢀproduct due to the competing hydraꢀ
tion of 2a (Table 1, entry 5).9c Complex 1e is known to form
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digold hydroxide 1a in the presence of water.9b These results
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99% yield). The nature of the substituent on the aryl ring of
1
2
3
4
5
6
7
8
gave us confidence that a bifunctional catalyst enhanced reacꢀ
tivity. The solvent was found to also have an important
the benzoic acids had little influence on the reaction yield and
a variety of electronꢀdonating and withdrawing substituents
could be tolerated including bromo (3e, 3f and 3j), nitro (3c
and 3g), methoxy (3a and 3d), fluoro (3i) and even substituted
amine (3h) groups. The use of sterically hindered benzoic
acids did not affect the reaction rate and led to compounds 4aa
and 4al in high yields.
Table 1. Reaction Development of the Au(I)-Catalyzed
Addition of Carboxylic Acids to Alkynesa
OMe
OMe
CO2H
MeO
O
Ph
[Au]
Scheme 1. Hydrocarboxylation of diphenylacteylene 2a
with aryl and alkylcarboxylic acids
+
Ph
Ph
O
9
OMe
Ph
2a
3a
4aa
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R
Conversion
(%)b
1a (0.5 mol%)
O
Ph
Entry
Catalyst
Solvent
+
Ph
Ph
R
CO2H
O
80 °C
Ph
[{Au(IPr)}2(µꢀOH)] (1a)
1
Toluene
>99c,d
34c,d
40c,d
70c,d
0c,d
2a
3a-r
4aa-ar
(2 mol%)
[{Au(SIPr)}2(µꢀOH)] (1d)
2
3
4
5
Toluene
Toluene
Toluene
Toluene
R
Br
(2 mol%)
R
OMe
O
[Au(IPr)(OH)] (1c)
O
O
Ph
O
Ph
O
Ph
MeO
Ph
(4 mol%)
O
O
O
Ph
Ph
Ph
Ph
[Au(IPr)(MeCN)][BF4] (1e)
R = Br, 4af (90%, 10 h)
NO2, 4ag (>99%, 10 h)
NMe2, 4ah (93%, 19 h)
F, 4ai (60%, 15 h)
4aj
80%, 10 h
4aa
93%, 10 h
R = H, 4ab (94%, 15 h)
NO2, 4ac (74%, 5 h)a
OMe, 4ad (92%, 15 h)
Br, 4ae (90%, 15 h)a
(4 mol%)
[Au(IPr)(NTf2)] (1f)
(4 mol%)
O
6
7
8
1a (0.5 mol%)
1a (0.5 mol%)
Toluene
Neat
65
N
O
O
Ph
O
Ph
>99 (93%)
93%
O
Ph
O
O
Ph
Ph
O
O
O
1c (0.5 mol%) + 1e (0.5 mol%)
Neat
Ph
Ph
Ph
4am
83%, 15 h
4ak
84%, 24 ha,b
4al
>99%, 15 h
4an
89%, 5 h
aConditions: alkyne (0.5 mmol), carboxylic acid (0.5 mmol),
solvent (1 M), 80 °C, 16 h. bConversion determined by GC.
c2a/3a (1.1/1). d85 °C.
Ph
H
O
O
Ph
O
Ph
O
Ph
O
O
Ph
O
O
influence on the course of the reaction with toluene being
optimal (see ESI for further optimization studies). Slower
reaction rate was observed with a 1/1 ratio of 2a/3a and a
further decrease of the catalyst loading to 0.5 mol% (Table 1,
entry 6). To reduce the environmental impact of the process,
the reaction was carried out under solventꢀfree conditions.
Gratifyingly, using 0.5 mol% of 1a, 74% conversion was
observed after 5 h and the reaction was complete after 10 h
affording (Z)ꢀvinyl ester 4aa in 93% yield without traces of
hydration sideꢀproduct (Table 1, entry 7). As previously menꢀ
tioned, digold hydroxide 1a can be seen as the combination of
[Au(IPr)(OH)] 1c and [Au(IPr)][BF4] 1b. Since complex 1b is
not a stable species, 1e is generally used as a substitute. We
were pleased to see that using 0.5 mol% of both 1c and 1e led
to high conversion to vinyl ester 4aa (93%) as well (Table 1,
entry 8). This result strongly supports that 1a acts as a bifuncꢀ
tional catalyst for the hydrocarboxylation of alkynes. Remarkꢀ
ably, these conditions allow for a very simple and economical
workꢀup procedure; pentane is simply added to the crude
mixture and the pure vinyl esters can be isolated by filtration
without the need for chromatography or any further purifica-
tion. Precautions to exclude air are unecessary in this proceꢀ
dure.
Ph
Ph
Ph
Ph
4ao
95%, 5 h
4ap
94%, 5 h
4aq
90%, 2 h
4ar
88%, 4 h
10 mmol (92%, 6 h)
Reaction Conditions: Alkyne (0.5 mmol), carboxylic acid (0.5
mmol), [Au] (0.0025 mmol), 80 °C. Isolated yields. Average of
two runs. a110 °C. bUsing 1 mol% of 1a.
Pleasingly, the addition of heteroarylcarboxylic acids such
as 2ꢀpicolinic acid (3k) and furoic acid (3m) proceeded
smoothly without affecting the catalyst activity. Furthermore,
this methodology was also applicable to vinylcarboxylic acids
such as acrylic acid (3o) and cinnamic acid (3p) providing
access to compounds 4ao and 4ap, in short reaction times and
with excellent yields and complete chemoselectivity. This
reactivity is remarkable as acrylic acid is wellꢀknown to unꢀ
dergo very facile polymerization. Gratifyingly, the methodolꢀ
ogy could be extended to several aliphatic carboxylic acids.
The reactions with these substrates proceeded much faster,
most likely due to their enhanced nucleophilicity, and without
any loss of stereoselectivity, forming the product (Z)ꢀisomer
only. Both formic acid (3q) and acetic acid (3r) were also
successfully converted in high yields to the corresponding
vinyl esters. It is worth mentioning that, to date, vinyl acetate
has only been obtained in a maximum of 62% yield using
alternative methodologies.5j Also, the particular stability of
vinyl acetate, under these conditions, is remarkable as this
compound easily polymerize to polyvinyl acetate ꢀ one of the
industrially most important homopolymer.11 Finally, a reaction
was conducted on a 10 mmolꢀscale (1.78 g of 2a), a 92% yield
With the optimized conditions in hand, the scope of the reꢀ
action was initially explored using diphenylacetylene 2a and a
wide variety of carboxylic acids (Scheme 1). The methodoloꢀ
gy proved to be broadly applicable and a diverse range of
vinyl esters could be synthesized with complete stereoselectivꢀ
ity. Therefore, a series of functionalized (Z)ꢀdiphenylvinyl
benzoates could be obtained in good to excellent yields (60ꢀ
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dinate to the alkyne 2 to form πꢀgoldꢀalkyne complex I,12
(2.19 g) of (Z)ꢀ1,2ꢀdiphenylvinylacetate 4ar could be sucꢀ
cessfully isolated after simple filtration.
1
2
3
4
5
6
7
8
while the latter would deprotonate the carboxylic acid 3 to
generate gold carboxylate II.13 In a parallel scenario, digold
hydroxide 1a could directly react with carboxylic acid 3 to
Encouraged by these results, the reactivity of both symmetꢀ
rical and unsymmetrical alkynes with benzoic acid (3b) was
next examined (Scheme 2). Interestingly, the reactions were
found to be faster with unsymmetrical than symmetrical alꢀ
kyne substrates. In general, good to complete regioselectivities
were observed using unsymmetrical alkynes with the addition
of benzoic acid 3b occurring at the most electrophilic carbon
of the triple bond.
Scheme 3. Proposed mechanism
H
O
BF4
- H2O, + 3
[{Au(IPr)}2(ꢀ-O2CR)][BF4]
(IPr)Au Au(IPr)
(1a)
III
(2)
(3)
R'
R"
+
H2O
R CO2H
- H2O
2
9
RCO2 R"
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Scheme 2. Addition of benzoic acid to unsymmetrical in-
ternal alkynes
R'
(4)
BF4
[Au]
RCO2 R"
R'
R"
I
R'
[Au]
Ph
O
Ph
O
2 + 3
[Au] = [Au(IPr)]
V
O
R2
O
R1
[Au(IPr)(O2CR)]
1a (0.5 mol%)
R1
R2
+
Ph CO2H
II
R1
4bb-ib
R2
4bb'-ib'
80 °C
2b-i
3b
BF4
R"
[Au]
[Au]
IV
RCO2
R'
Ph
Ph
O
Ph
O
O
Ph
O
nPr
O
CO2Et
CO2Me
O
Ph
O
O
form digold carboxylate III. This species, in the presence of
alkyne 2, would be in equilibrium with I and II. From this
point, subsequent nucleophilic attack of gold carboxylate II
toward πꢀcomplex I in an antiꢀfashion would lead to the forꢀ
mation of gemꢀdiaurated species IV14 or σꢀmonoaurated speꢀ
cies V,15 most likely in equilibrium – the former being rather
an offꢀcycle species.14bFinally protodeauration with either H2O
or carboxylic acid would deliver the final vinyl ester 4. This
represents the possibilities enabling the transformation. Efforts
aimed at clarifying the exact mechanistic route leading to
product are presently being carried out in our laboratory.
nPr
4bb
98%, 16 h
Ph
4eb
87%, 6 h
MeO2C
4cb
4db
86%, 19 h
99%, 1.5 h
Ac
Ph
O
O
Ph
Ph
O
Ph
O
O
Ph
O
OBn
O
O
Ph
Et
Ph
4fb
4gb
4ib
>99%, 16 h
4hb
89%, 19 ha
94 % (1:0.27), 8.5 h
95% (1:0.25), 2 h
Reaction Conditions: Alkyne (0.5 mmol), carboxylic acid (0.5
mmol), [Au] (0.0025 mmol), 80 °C. Isolated yields. Average of
two runs. Ratio determined by 1H NMR. aUsing 1 mol% of 1a.
In summary, we have developed a straightforward and highꢀ
ly efficient methodology for the hydrocarboxylation of interꢀ
nal alkynes catalyzed by a digold hydroxide complex enabling
the formation of various aryl and alkyl vinylesters in good to
excellent yields with superb regioꢀ, chemoꢀ and stereoselectivꢀ
ity. In addition, the use of solventꢀfree conditions not only
permits a practical, operationally simple and scalable strategy
but leads to faster reaction kinetics. The present process repreꢀ
sents a practical and atomꢀeconomical alternative to existing
synthetic methods to assemble vinyl ester motifs that are not
easily accessed. Further studies aimed at extending the reacꢀ
tion scope and at exploring the potential use of 1a in other
transformations are currently underway.
Under our previous conditions, both 4ꢀoctyne (2b) and diꢀ
methylacetyldicarboxylate (DMAD) (2c) were successfully
converted, again with complete stereoselectivity, to vinyl ester
(4bb) and dimethyl fumarate (4cb) in high yields. Remarkaꢀ
bly, the reactions of both phenylpropyne (2c) and pheꢀ
nylpropiolate (2d) afforded the vinyl esters (4db) and (4eb) in
complete regioꢀ and stereoselectivity. Diarylꢀsubstituted alꢀ
kyne 2f underwent hydrocarboxylation with good regioselecꢀ
tivity. Similarly, good regioꢀ and complete chemoselectivity
was obtained when reacting enyne 2g. Finally, total converꢀ
sion of unsymmetrical alkynes 4h and 4i into vinyl esters 4hb
and 4ib was achieved with complete regioꢀ and stereoselectiviꢀ
ty.
ASSOCIATED CONTENT
Next, the recyclability of the catalyst was assessed. Formic
acid 4q and diphenylacetylene 2a substrates were chosen as
the test reaction for sake of expediency. Once the reaction was
complete, iterative additions of both substrates were perꢀ
formed. As a result, 6.5 mmol of 2a was converted to 4aq
using 2.5 µmol of 1a, affording an exceptional turnover numꢀ
ber (TON) of 2610 for this reaction (compared to a TON of 18
reported in ref 5j). This attests to the robustness of the catalytꢀ
ic system as once again no precaution to exclude air and moisꢀ
ture was taken.
Supporting Information. Optimization studies, experiꢀ
mental procédures, characterization data for all the comꢀ
pounds. This material is available free of charge via the
Internet at http://pubs.acs.org
AUTHOR INFORMATION
Corresponding Author
stevenpnolan@gmail.com
Notes
On the basis of previous mechanistic studies,9b the following
mechanism can be proposed for the gold(I)ꢀcatalyzed hydroꢀ
carboxylation of alkynes (Scheme 3).
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Two initiation steps can be envisaged. In a dual activation
mode, 1a would dissociate into Lewis acid [Au(IPr)][BF4] 1b
and Brønsted base [Au(IPr)(OH)] 1c. The former would coorꢀ
The ERC is gratefully acknowledged for support. Umicore
AG is acknowledged for their generous gift of materials.
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75, 7928; (k) Wang, Y.; Wang, Z.; Li, Y.; Wu, G.; Cao, Z.; Zhang, L.
Nat Commun 2014, 5, 1.
The EPSRC National Mass Spectrometry Service Centre is
gratefully acknowledged for HRMS data.
1
2
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R
O
[Au] (0.5 mol%)
R2
R1
R2
+
R
OH
R1
26 examples
(60ꢁ99% yield)
Cooperative catalysis
BF4
H
O
(IPr)Au
Au(IPr)
Solvent-free conditions
No additive
No purification needed
Regio- and stereospecific
[Au(IPr)][BF4]
[Au(IPr)(OH)]
+
Lewis acid
Brønsted base
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