Regio- and Stereoselective Hydrosulfonylation of Electron-Deficient Alkynes: Access to Both E- and Z-β-Sulfonyl-α,β-Unsaturated Carbonyl Compounds

Article abstract of DOI:10.1002/adsc.201801032

A metal-free hydrosulfonylation of electron-deficient alkynes with sodium sulfinates or sulfinic acids to access both E- and Z-β-sulfonyl-α,β-unsaturated carbonyl compounds has been developed. We propose that this reaction via a hydroxylallene intermediate delivers the thermodynamically stable E isomer, or via a concerted termolecular Ad_E3 mechanism affords Z isomer. The stereoselectivity of addition (syn or anti) can be controlled by varying the sulfonyl sources and acidic buffer solutions. This protocol exhibits broad substrate scope for internal or terminal alkynes including various substituted ynones and alkynyl esters. This approach is mild, efficient, operationally simple and easy to be scaled-up. (Figure presented.).

Full text of DOI:10.1002/adsc.201801032

Title: Regio- and Stereoselective Hydrosulfonylation of Electron-
Deficient Alkynes: Access to Both E- and Z-β-Sulfonyl-α,β-
Unsaturated Carbonyl Compounds
Authors: Wei Zhang, Gabriel M. Johnson, Zhi Guan, and Yan-Hong He
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Regio- and Stereoselective Hydrosulfonylation of Electron-
Deficient Alkynes: Access to Both E- and Z-β-Sulfonyl-α,β-
Unsaturated Carbonyl Compounds
Wei Zhanga, Gabriel M. Johnsonb, Zhi Guana*, Yan-Hong Hea*
aKey Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering,
Southwest University, Chongqing 400715, China
bChemistry Department, College of Saint Benedict and Saint John’s University, MN 56374, USA
Fax: (+86)-23-68254091; E-mails: guanzhi@swu.edu.cn (for Z. Guan); heyh@swu.edu.cn (for Y.-H. He)
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######
Abstract: A metal-free hydrosulfonylation of electron- This protocol exhibits broad substrate scope for internal or
deficient alkynes with sodium sulfinates or sulfinic acids to terminal alkynes including various substituted ynones and
access both E- and Z-β-sulfonyl-α,β-unsaturated carbonyl alkynyl esters. This approach is mild, efficient,
compounds has been developed. We propose that this operationally simple and easy to be scaled-up.
reaction via a hydroxylallene intermediate delivers the
thermodynamically stable E isomer, or via a concerted
termolecular AdE3 mechanism affords Z isomer. The
stereoselectivity of addition (syn or anti) can be controlled
by varying the sulfonyl sources and acidic buffer solutions.
Keywords: hydrosulfonylation; E- and Z- stereoselectivity;
β-sulfonyl-α,β-unsaturated carbonyl compounds; AdE3
mechanism
sulfones can serve as versatile synthetic precursors[8]
in organic synthesis. For example, they are efficient
Michael acceptors,[9] as well as elegant 2π partners in
cycloaddition reactions.[10] Consequently, it is highly
desirable to develop concise and efficient
methodologies for the synthesis of vinyl sulfones,
especially for the synthesis of β-sulfonyl-α,β-
unsaturated carbonyl compounds, which are
important sources of highly functional vinyl sulfones.
According to the literature, different routes are
available for the synthesis of β-sulfonyl-α,β-
unsaturated carbonyl compounds. Traditionally, they
are synthesized by the nucleophilic substitution of
sodium sulfinates to 2-chlorovinyl ketones.[11]
Further, they can be prepared by eliminating
Introduction
Construction of sulfur-containing organic compounds
with sustainable and green methods has received
significant attention because C-S bond is ubiquitous
in many natural products and pharmaceutical
compounds.[1] As highly valuable organosulfur
compounds, vinyl sulfones have gained intensive
interest due to their prominent biological activities[2]
and synthetic versatility.[3] On the one hand, they not
only possess a wide range of pharmacological
properties such as antibacterial,[4] antifungal[5] and
antitumor activities[6] but also exhibit important
biological activities which are known to inhibit
different enzymes.[7] On the other hand, vinyl
1
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
hydrogen bromide of the bromo derivatives of
because the Z/E configuration of the vinyl group can
often result in different biological activities,
pharmacological activities and photochromic
properties.[20] Accordingly, Development of mild and
practical methods for the synthesis of both E and Z
functional vinyl sulfones with high stereoselectivity
is highly desirable. Herein, we are glad to present a
unique Brønsted acid catalytic system for
hydrosulfonylation of electron-deficient alkynes
using sodium sulfinates or sulfinic acids. With this
method, both E- and Z-β-sulfonyl-α,β-unsaturated
carbonyl compounds can be easily prepared with high
stereoselectivity at will.
saturated
keto
sulfones.[12]
Oxidation
of
corresponding sulfides or sulfoxides also is an
alternative synthetic method for their preparation.[8,13]
However, these procedures require multiple steps and
suffer from either narrow substrate scope or poor
stereoselectivity. Therefore, there is still a demand for
straightforward stereoselective methods for the
preparation of β-sulfonyl-α,β-unsaturated carbonyl
compounds. Indeed, the selective access to E-β-
sulfonyl-α,β-unsaturated carbonyl compounds has
been achieved with Pd catalysts: Jiang’s group
reported the palladium-catalyzed coupling of alkynes
with sodium benzene sulfinate to form E sulfones
(Scheme 1a),[14] and Li’s group reported the
conjugate addition of alkynes with 1,2-
bis(phenylsulfonyl)ethane in the presence of
Pd(OAc)2 to get E sulfones (Scheme 1b).[15] For
metal-free systems, a concise route to 1,3-diphenyl-3-
tosylprop-2-en-1-one via the addition of sodium p-
toluenesulfinate to 1,3-diphenylprop-2-yn-1-one has
been described, but the product was obtained as a
mixture of Z and E isomers (Scheme 1c),[16]
Moreover, an alternative approach which gives
selective access to Z-β-sulfonyl-α,β-unsaturated
carbonyl compounds has been developed by Wang
and co-workers through the reaction of β-hydroxy-β-
phenyl-α-diazo ketones and glyoxylic acid chloride p-
Scheme 1. Approaches to β-sulfonyl-α,β-unsaturated
carbonyl compounds
Results and Discussion
In our initial investigation, the ynone (1a) was used
as a model substrate to react with PhSO2Na in EtOH
at room temperature for 18 h. The reaction provided
β-sulfonyl-α,β-unsaturated carbonyl compounds 2a
and 3a with a poor yield (13% yield, E/Z = 93:7,
Table 1, entry 1). Surprisingly, when PhSO2H was
used instead of PhSO2Na in the reaction, the
selectivity of this reaction was inversed, and the
products 2a and 3a were obtained with a higher yield
(26% yield, E/Z = 2:98, Table 1, entry 10). Inspired
by the result that varying the sulfonyl sources led to
toluenesulfonylhydrazones
(Scheme
1d).[17]
However, direct access to both stereoselective E- and
Z-β-sulfonyl-α,β-unsaturated carbonyl compounds is
still challenging. Although a few elegant examples of
preparing both stereoisomers of substituted olefins
were achieved with the aid of heteropoly compound’s
catalysis,[18] or hydrogen-bonding-assisted Brønsted
acid and gold catalysis.[19] Stereoselective access to
highly functional vinyl sulfones is often the pivotal
factor in the success of any vinyl sulfone synthesis
2
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
different E/Z selectivity, we made efforts to optimize
the reaction for selective synthesis of both E- and Z-
β-sulfonyl-α,β-unsaturated carbonyl compounds.
achieve E selective product 2a by using PhSO2Na as
the sulfonyl source. Screening several common
organic solvents indicated that solvents had an
important influence on the stereoselectivity of the
reaction. Generally, E stereoselectivity increased with
increasing solvent polarity (Table 1, entries 1-5). The
best selectivity was obtained in ethanol, but a
competitive side reaction of ethoxyl addition
occurred in ethanol. Thus, considering both yield and
selectivity, we chose DMF as the optimal solvent.
Furthermore, it was found that adding water to the
reaction system was beneficial for improving the
stereoselectivity of the reaction (Table 1, entry 6),
probably because the addition of water increased the
polarity of the solvent. Taking into consideration that
the acid-base properties of sulfonyl sources have a
significant effect on the stereoselectivity of this
sulfonated reaction, we tested the influence of
different acids and bases on the reaction; it was found
that the yield and selectivity can be remarkably
improved (89% yield, E/Z = 95:5) in the presence of
AcOH and K2CO3 (for details, please see SI, Table
S1). To pursue even better results, we then screened a
series of buffer solutions with different pH (Table 1,
entries 7-9. For details including the preparation of
buffer solutions, please see SI, Table S2). Finally,
acetate buffer solution (pH = 3.5) was found to be
superior to any other explored buffer solutions; it
provided a satisfactory result (97% yield, E/Z = 99:1,
Table 1, entry 9).
Table 1. Optimization of reaction conditions.[ a]
Entry Solvent
Sulfonyl
source
PhSO2Na
Note
(pH)
--
Yield(%)[b]
(2a:3a)[c]
13 (93:7)
1
2
EtOH
DCM
PhSO2Na
--
--
--
--
--
11(70:30)
16 (68:32)
33 (85:15)
51 (83:17)
48 (87:13)
59 (98:2)
3
Toluene PhSO2Na
4
MeCN
DMF
DMF
DMF
PhSO2Na
PhSO2Na
PhSO2Na
PhSO2Na
5
6[d]
7[e]
PBS
(5.2)
8[e]
DMF
PhSO2Na
BR
67 (96:4)
buffer[f]
(4.5)
9[e]
DMF
PhSO2Na
Acetate 97 (99:1)
buffer
(3.5)
10
11[g]
EtOH
EtOH
PhSO2H
PhSO2H
--
26 (2:98)
Acetate 84(7:93)
buffer
(3.5)
BR
buffer
(3.5)
BR
12[g]
EtOH
PhSO2H
99 (4:96)
13[g]
DMF
PhSO2H
96 (23:77)
buffer
(3.5)
[a]
Reaction conditions: 1a (0.15 mmol), sulfonyl source
(0.30 mmol), and solvent (1.0 mL) at rt for 18 h (for entries
1-10) or 40 h (for entries 11-13).
[b] Isolated yield.
1
[c] 2a/3a ratios were determined by H NMR spectroscopy
and HPLC analysis.
We then focused our attention on optimization of
reaction conditions for the selective preparation of Z
isomer (3a) by using PhSO2H as the sulfonyl source.
By the process of optimizing the reaction for the
synthesis of E isomer (2a) we realized that buffer
[d] DMF (0.7 mL) and H2O (0.3 mL).
[e] DMF (0.7 mL) and buffer solution (0.3 mL).
[f]
BR (Britton-Robinson) buffer solutions of various pH
were prepared by mixing appropriate volumes of acid
buffer component (0.04 M H3PO4, 0.04 M AcOH and 0.04
M H3BO3) with basic buffer component (0.2 M NaOH).
[g] Solvent (1.0 mL) and buffer solution (0.3 mL).
solutions
have
an
important
impact
on
stereoselectivity of this reaction. Thus, we evaluated
the effect of buffer solutions with different pH (Table
We first optimized the reaction conditions to
3
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
1, entries 11-13; for details, please see SI, Table S3).
Ultimately, we found that in the presence of BR
buffer (pH = 3.5), the reaction in ethanol can give an
excellent result (99% yield, Z/E = 96:4, Table 1,
entry 12), while the reaction in DMF gave a lower
selectivity (96% yield, Z/E = 77:23. Table 1, entry
13). Therefore, ethanol/BR buffer (pH = 3.5) was
selected as the suitable reaction medium for the
selective preparation of Z isomer. It is worth
mentioning that in the case of using PhSO2H, no
competitive reaction of ethoxyl addition was
observed in ethanol, which may be due to the
inhibition of this side reaction in the acidic reagent.
Above experiments showed that ethanol as solvent
can give good stereoselectivity for both E- and Z-
products (Table 1, entries 1 and 10). When PhSO2Na
was used, an E-selective product was mainly
obtained, and when PhSO2H was used, the Z-
selective product predominated. Therefore, we think
that sulfonyl sources may be the major origin of the
stereoselectivity.
Encouraged by these satisfactory results, we
attempted to explore the substrates which were
substituted by alkoxy, alkyl and alkenyl. Alkynyl
ester could be converted into the desirable product in
somewhat diminished yield and stereoselectivity (2l).
This may be due to the electron-donating nature of
the ethoxyl group which reduces the reactivity of the
substrate. Pleasingly, the alkyl and alkenyl substituted
substrates could be readily converted by this method
(2m and 2n). Furthermore, we extended the substrate
scope to ynones with different substituents at alkyne
end. The efficiency of this conversion was almost
unaffected by the electronic property. Both electron-
rich (4-Me, 4-OMe) and electron-deficient (4-F, 4-Cl)
ynones were good reaction partners, giving good
yields and prominent stereoselectivity (2o-2s).
Moreover, the remarkable generality and efficacy of
this protocol was demonstrated on a range of ynones
in which the phenyl moieties at both ends were
substituted at different positions by substituents of
different electronic nature (2t-2v). Good result was
also obtained when the alkyne end was substituted
with n-butyl, which showed good substrate suitability
(2w). Ultimately, various sodium sulfinates including
both sodium arylsulfinates and alkylsulfinates were
also subjected to this protocol (2x-2z and 2aa). But
unfortunately, 3-phenylpropiolic acid, chalcone and
sodium trifluoromethanesulfinate etc. resisted
participating in the reaction (for details, please see SI,
Scheme S1). The E configuration of 2a was
confirmed by single-crystal X-ray analysis (Fig. 1). It
Next, the optimized conditions (Table 1, entry 9)
were adopted to selectively prepare E isomers of β-
sulfonyl-α,β-unsaturated carbonyl compounds. We
probed the feasibility of substrate scope, and the
results are summarized in Table 2. In general, a series
of ynone derivatives with diverse substitution
patterns on benzene ring at the keto terminal of
ynones could react smoothly to afford the desired
products in moderate to good yields with good
stereoselectivity (2b-2i). Both electron-donating (Me)
and electron-withdrawing (Cl, CF3, CO2Me, etc.)
groups were well tolerated. The substitution position
had a slight effect on the efficiency of this
transformation (2b-2d). Moreover, naphthyl and
thienyl substituted ynones also could serve as suitable
reaction partners giving corresponding products with
good yields and excellent selectivity (2j and 2k).
1
has a characteristic single peak at δ 7.98 ppm on H
NMR spectrum which is the signal of alkenyl proton.
Moreover, product 2l (71:29 E/Z) has the
characteristic single peak of alkenyl proton at δ 7.59
(E isomer) which is consistent with the literature; [21]
All the products in Table 2 have a characteristic
single peak of alkenyl proton at δ 8.13 – 7.58 ppm, so
4
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
we assigned them as E configuration. As a
representative, assignment of configuration of
products 2m and 2n is demonstrated in SI (see S3).
demonstrated outstanding functional group tolerance.
We observed that product 3l was furnished just in a
moderate yield, which may be due to its poor
solubility under standard conditions. The internal and
terminal alkynyl groups of alkynyl esters could be
converted accordingly (3p and 3q). Both but-3-yn-2-
one and pent-3-yn-2-one as suitable reaction partners
delivered the desired products with excellent yields
and good stereoselectivity (3r and 3s). Moreover,
alkyl sulfinic acid and p-chlorophenyl sulfinic acid
were also amenable to this protocol giving good
results (3t and 3u). The Z configuration of 3a was
confirmed by single-crystal X-ray analysis (Fig. 1). It
Table 2. Substrate scope for the synthesis of E-β-sulfonyl-
α,β-unsaturated carbonyl compounds.[a]
1
has a characteristic single peak at δ 6.82 ppm on H
NMR spectrum which is the signal of alkenyl proton.
All the products in Table 3 (except 3q-3s which are
known compounds[22]) have a characteristic single
peak of alkenyl proton at δ 6.94 – 6.43 ppm. Thus, we
assigned them as Z configuration. As a representative,
assignment of configuration of product 3i is
demonstrated in SI (see S3).
Table 3. Substrate scope for the synthesis of Z-β-sulfonyl-
α,β-unsaturated carbonyl compounds.[a]
[a]
Reaction conditions: 1 (0.15 mmol), RSO2Na (0.30
mmol), DMF (0.7 mL), acetate buffer solution (pH =3.5,
1
0.3 mL), rt for 18 h. E/Z ratios were determined by H
NMR spectroscopy.
[b] PhSO2H (0.30 mmol) and K2CO3 (0.15 mmol) instead of
PhSO2Na, DMF (0.7 mL)/H2O (0.3 mL).
[c] Reaction for 40 h.
We then investigated the substrate scope of the
reaction for the selective synthesis of Z isomer of β-
sulfonyl-α,β-unsaturated carbonyl compounds, as
outlined in Table 3. Because of mild conditions and
high reactivity, all employed electron-deficient
alkynes were found to be compatible substrates
resulting in satisfactory yields and good
stereoselectivity (3a-3u). Moreover, the reaction
5
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
[a]
Reaction conditions: 1 (0.15 mmol), RSO2H (0.30
mmol), EtOH (1.0 mL), BR buffer solution (pH = 3.5, 0.3
1
mL), rt for 40 h. Z/E ratios were determined by H NMR
spectroscopy.
[b]
PhSO2H (0.45 mmol).
[c ] Reaction for 72 h.
Scheme 2. Scalable synthesis and further transformations
of β-sulfonyl-α,β-unsaturated carbonyl compounds
In order to gain more information of this
hydrosulfonylation reaction, a series of control
experiments were performed (Scheme 3). It is well-
known that ynones are good radical receptors[24] and
benzene sulfinic acid is easily oxidized by oxygen to
produce a sulfonyl radical.[25] In order to verify
whether this hydrosulfonylation reaction refers to a
radical process, the radical inhibition experiments
with the radical scavengers 2,2,6,6-tetramethyl-1-
piperidinyloxy (TEMPO) and 2,4-di-tert-butyl-4-
methylphenol (BHT) were conducted. The progresses
of generating desired products were almost
unaffected and no observable radical intermediates
were trapped (Scheme 3a and 3b). Moreover, when
the reaction was carried out under argon atmosphere,
this transformation proceeded very well to afford the
desired product (Scheme 3c). On the basis of these
experimental results we concluded that a radical
process could be ruled out. Taking into consideration
that ynones are good Michael acceptors[22,26] and
benzene sulfinic acid is a good nucleophilic reagent,
we speculated that this transformation may involve a
nucleophilic addition process. The experiment in
which ethanol as a nucleophilic reagent could react
with ynone 1a successfully supported this hypothesis
(Scheme 3d). Next, we turned our attention to probe
whether the Z isomer was obtained via an
isomerization of E isomer. The kinetic experiments of
Z isomer revealed that the ratio of Z isomer and E
Fig. 1. X-ray crystal structures of 2a (E, left) and 3a (Z,
right)
A gram-scale reaction of 1a was next conducted to
check the synthetic potential of this methodology.
Gratifyingly, similarly good yields and excellent
stereoselectivity were obtained for both 2a and 3a at
a larger scale (Scheme 2, eq 1). To demonstrate the
potential utility of this method and probe the
differences in properties of Z and E isomers, several
transformations of 2a and 3a were explored (Scheme
2, eq 2 and eq 3). 2a could be readily converted into
acetyl hydrazone 4 in a moderate yield under mild
reaction conditions. Interestingly, we found that 3a
was also similarly converted into 4, probably due to
the isomerization of 3a under this reaction conditions.
Additionally, under ultrasound (US) irradiation
conditions pyrazole derivative 5 could be efficiently
obtained from 2a, while 3a was transformed into
unsaturated α-amino ketone 6 with a good yield (the
structure of 6 was confirmed by single-crystal X-ray
analysis, see SI, S7 crystallographic analysis). These
examples exhibited a diversified application of β-
sulfonyl-α,β-unsaturated carbonyl compounds in the
preparation of various precursors of biologically
active molecules.[23]
6
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
isomer was constant over time under standard
reaction conditions (please see SI, Figure S1).
Therefore, the inversion of configuration may not be
involved.
approximately 2. This result supports the proposed
mechanism (for details of kinetic study and analysis
of possible factors affecting the determination of
reaction order, see SI, S7).
Scheme 4. Plausible mechanism
Conclusion
In summary, we have successfully developed an
efficient approach for the hydrosulfonylation of
electron-deficient alkynes to access both E and Z-β-
sulfonyl-α,β-unsaturated carbonyl compounds. The
procedure results in good yields and high
stereoselectivity with various substituted ynones or
alkynyl esters, and it shows good functional-group
tolerance. Based on this unique Brønsted acid
catalytic system of acidic buffer solutions, a series of
β-sulfonyl-α,β-unsaturated carbonyl compounds can
be prepared at room temperature. Moreover, the
potential utilities of this method and the differences in
properties of Z and E isomers have been explored,
and an efficient approach to synthesize pyrazole
derivative and unsaturated α-amino ketone was
obtained.
Scheme 3. Control experiments
On the basis of the aforementioned experimental
results and previous reports,[19d,27]
a plausible
mechanism of this hydrosulfonylation reaction is
proposed shown in Scheme 4. When a sulfinate is
used, it acts as a highly reactive sulfonyl nucleophile
to directly attack the ynone 1a generating
intermediate I. I receives a proton from the reaction
system affording hydroxylallene intermediate II,
which undergoes conversion of enol to ketone
delivering the thermodynamically stable syn-addition
product (E isomer) 2a (Scheme 4a). On the other
hand, when a sulfinic acid is used as the sulfonyl
source which acts as a less active sulfonyl
nucleophile than sulfinate, the direct nucleophilic
addition is more difficult. Thus, we propose a
Experimental Section
concerted
termolecular
AdE3
mechanism.
Nucleophile sulfinic acid activates ynone 1a to
promote the hydrosulfonylation reaction, leading to
the formation of the anti-addition product (Z isomer)
3a (Scheme 4b). We performed a kinetic study on the
reaction that produces the Z isomer. The order of the
sulfinic acid was measured to be 1.69, which is
General procedure for the synthesis of E-β-sulfonyl-α,β-
unsaturated carbonyl compounds (2): A round-bottom flask
was charged with ynone 1 (0.15 mmol), RSO2Na (0.3
mmol), DMF (0.7 mL) and acetate buffer solution (pH =
3.5, 0.3 mL). The resultant mixture was stirred at room
temperature and monitored by thin-layer chromatography
(TLC) using UV light and vanillic aldehyde as visualizing
7
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10.1002/adsc.201801032
Advanced Synthesis & Catalysis
agents. Upon completion of the reaction, the mixture was
diluted with water (10 mL), and then extracted with ethyl
acetate (3 × 20 mL). The organic phase was dried over
anhydrous Na2SO4 and the organic solvent was removed
under reduced pressure. The crude products were purified
by flash column chromatography (ethyl acetate/petroleum
ether) to give the desired E-β-sulfonyl-α,β-unsaturated
carbonyl compounds (2).
Dunbar, D. H. Scharf, A. Litomska, C. Hertweck,
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General procedure for the synthesis of Z-β-sulfonyl-α,β-
unsaturated carbonyl compounds (3): A round-bottom flask
was charged with ynone 1 (0.15 mmol), RSO2H (0.3
mmol), EtOH (1.0 mL) and BR buffer solution ( pH = 3.5,
0.3 mL). The resultant mixture was stirred at room
temperature and monitored by thin-layer chromatography
(TLC) using UV light and vanillic aldehyde as visualizing
agents. Upon completion of the reaction, the mixture was
neutralized by saturated aqueous of Na2CO3 and then
extracted with ethyl acetate (3 × 20 mL). The organic
phase was dried over anhydrous Na2SO4 and the organic
solvent was removed under reduced pressure. The crude
products were purified by flash column chromatography
(ethyl acetate/petroleum ether) to give the desired Z-β-
sulfonyl-α,β-unsaturated carbonyl compounds (3).
[4] B. A. Frankel, M. Bentley, R. G. Kruger, D. G.
McCafferty, J. Am. Chem. Soc. 2004, 126, 3404-3405.
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FULL PAPER
Regio- and Stereoselective Hydrosulfonylation of
Electron-Deficient Alkynes: Access to Both E- and
Z-β-Sulfonyl-α,β-Unsaturated Carbonyl
Compounds
Adv. Synth. Catal. Year, Volume, Page – Page
Wei Zhang, Gabriel M. Johnson, Zhi Guan*, Yan-
Hong He*
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