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REVIEW
Recent advances in the synthesis of vinyl sulfones

Published on 15 June 2016. Downloaded by University of Kentucky on 16/06/2016 15:26:43.
Yuyu Fang, Zaigang Luo* and Xuemei Xu
RSC Advances Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx Development of methodology for the preparation of vinyl sulfones is of significant interest to organic chemists. Recently,
numerous useful methods have been developed, mainly including direct sulfonylation of olefins and alkynes,
DOI: 10.1039/x0xx00000x
decarboxylative sulfonylation of α,β-unsaturated carboxylic acids and decomposition of tosylhydrazones. This review will
www.rsc.org/ focus on recent achievements in vinyl sulfones synthesis and the mechanisms of the reactions are also discussed.
have been predominantly utilized, probably due to their good

1. Introduction stability and ease of handling.
Organosulfur compounds do not only contain fundamental
functional groups, such as thiol, sulfide, or disulfide units, which COOH
render them useful synthetic intermediates, but they also exist X
R1
abundantly in biological systems ranging from small natural R1
"S"
metabolites to proteins. Thus the formation of C-S bonds is one of R1 "S"
1 "S"
the fundamental transformations in organic synthesis. In recent O
O Ts
years, vinyl sulfones have attracted considerable interests in the
"S" S R Decomposition
NH
area of synthetic organic chemistry, owing to their important role in N
2
serving as key structural units of many biological active compounds R1 R1 R1
as well as versatile building blocks for various organic "S"
3 "S"
transformations. Therefore, considerable effort has been devoted R1
OAc
to the development of new and efficient methods for the synthesis "S" N
of vinyl sulfones. Over the past three decades, various classic COOH R1
R1 O
synthetic routes to the vinyl sulfone skeleton have been developed,
such as the Knoevenagel condensations of sulfonylacetic acids with "S" sulf one sources
4
aromatic aldehydes, Horner-Wadsworth-Emmons reactions of
5
sulfonyl phosphonates and carbonyl compounds, β-elimination of
6
halosulfones or selenosulfones, and oxidation of the corresponding RSO 2Na RSO 2NHNH 2 RSO 2H RSH DMSO.....
7
vinyl sulfides. However, most of these methods suffer from some
limitations, such as inaccessible starting materials, tedious Scheme 1 Recent protocols for the synthesis of vinyl sulfones
procedures, relatively harsh reaction conditions, or generation of
large amounts of unwanted byproducts. Hence, the development of The synthetic power of the vinyl sulfone functional group has
efficient methods for the preparation vinyl sulfone scaffolds is been substantially upgraded over the past 30 years. Previous
desirable. seminal reviews provided by Fuchs, Forristal, Gervay-Hague,
Recently, the direct cross-coupling of the sulfonyl derivative with Carretero, Pathak, and so on, are out-of-date.8 In most cases, the
an alkene or alkyne source has emerged rapidly as an efficient list of reviews cited in this article is an indication of the usefulness
protocol for the construction of vinyl sulfones (Scheme 1). of the vinyl sulfone group and its popularity with the practising
Generally, the facile sulfone sources could be originated from organic chemists. Thus, an updated review focused on recent
sodium sulfinate, sulfonyl hydrazide, sulfinic acid, thiols, DMSO and achievements in vinyl sulfones synthesis as well as discussion of the
so on (Scheme 1), of which sodium sulfinate and sulfonyl hydrazide mechanisms of the reactions, would enrich the arsenals of synthetic
chemists who are interested in using vinyl sulfone groups in
synthetic transformations. In order to restrict the topic to a
College of Chemical Engineering, AnHui University of Science and Technology, manageable level, the primary organizational focus of this review
Huainan 232001, P. R. China. will relate mainly to direct sulfonylation of olefins and alkynes,
Email: luozi139@163.com
† Footnotes rela)ng to the )tle and/or authors should appear here.
decarboxylative sulfonylation of α,β-unsaturated carboxylic acids
Electronic Supplementary Information (ESI) available: [details of any and decomposition of tosylhydrazones in last 5 years. The cited
supplementary information available should be included here]. See articles were extensively selected from various journals and patents
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
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ARTICLE Journal Name
are not covered in this review. In addition, we sincerely hope that I2 (1.5 equiv)
SO2 Na NaOAc (1.5 equiv) R Ts
this review will serve as a handy reference for chemists interested H R
MeCN, reflux, 1h I
in organic alkenyl chemistry and discovering novel and efficient
methods for the preparation of vinyl sulfone building blocks. O2 N MeO
Ts Ts Ts Ts
2. Sulfonylation of alkynes
I I I I
2.1 Addition of sodium sulfinates to alkynes 74% 79% 82% 13%
The use of sodium salts of sulfinic acid as sulfonylation reagents has
9 Scheme 3 Molecular iodine-mediated β-iodosulfonation of sodium sulfinates
gained much attention in recent years. Sodium sulfinates are
stable, easy to handle and readily available from their with alkynes. TS, p-toluene sulfonyl .
10
corresponding sulfonyl chlorides. Recently, Jiang’s group

Oxidation CuX
RSO2 or RSO2 RSO2 Na RSO2 Cu
described a simple and efficient palladium-catalyzed cross-coupling
2 1 3
of sodium sulfinates and alkynes for the synthesis of vinyl sulfones R X R path B
(Scheme 2). This transformation proceeds under ligand-free and path A
ant i-addition sy n-addit ion
mild conditions, providing excellent yields of coupling products. The
X Cu SO2R
results suggest that electron-poor terminal alkynes, methyl H SO2R H
propiolate or ethyl propiolate provided the desired products in R SO2 R R R
4
higher yields. And substituted benzenesulfinic acid sodium salts, 2-
thienylsulfinic acid sodium salt, ethanesulfinic acid sodium salt or Scheme 4 Plausible mechanism of copper-catalyzed sulfonylation of alkynes
cyclopropanesulfinic acid sodium salt were successfully employed in with sodium sulfinates
this process, affording the desired products in good yields.
13
11
In 2013, Kuhakarn and co-workers reported an improved and Very recently, Moran and Rodríguez reported a facile access
into otherwise difficult to obtain alkyl alkynyl sulfones and cyclic
convenient experimental procedure to synthesize (E)-β-iodovinyl
vinyl sulfones via the reaction of alkyl sulfinates with
sulfones from alkynes by molecular iodine–mediated one-pot
alkynyl(aryl)iodonium salts (scheme 5). Alkynyl(aryl)iodonium salts
iodosulfonation (Scheme 3). The corresponding (E)-β-iodovinyl
can react with soft nucleophiles to generate alkylidene carbene
sulfones derived from phenylacetylene derivatives were obtained in
intermediates under aprotic conditions (Scheme 5). These carbenes
acceptable yields (74-82%) while poor yield was observed with that
can undergo 1,2-rearrangement to form a new alkyne or insert into
derived from aliphatic alkyne (13%). And the reaction was believed a C−H bond to form a five-membered ring. In this case, 1,2-
to mechanistically proceed via radical pathway. rearrangement is the exclusive reaction pathway when the sulfinate
Interestingly, Taniguchi12 displayed that copper-catalyzed contains a electron-withdrawing group.
sulfonylation of alkynes with sodium sulfinates in air afforded regio-
and stereoselectively (E)-vinyl sulfones (Scheme 4). When a CuCl Ph I X
O O
Et4 NBr (0.2 equiv) Ph S
catalyst was employed, the hydrosulfonylation proceeded syn- R R1 SO 2Na R1
CH 2Cl2/H 2O (3:1)
selectively, and (E)-alkenyl sulfones were synthesized. In contrast, O
R''
O S
the reaction using CuI catalyst produced (E)-β-haloalkenyl sulfones 1: R = H, X = OTs
2: R = OMe, X = OTs
Ph
anti-selectively in the presence of potassium halides. And the (E)-β- 3: R = H, X = O2 CCF3
bromoalkenyl sulfones are possible to convert into various alkenyl O O O O

O O
1: 32% Ph S 1: 52%
sulfones by Suzuki-Miyaura coupling. Ph S
2: 24%
Ph S 1: < 5%
2: 71%
2: 19%
3: 32% 3: 17% F3 C 3: 89%
O O O
O 1: 57% 1: 0%
PdCl2 (5mol%) O O S 1: < 5% O S
O S CF3
R1 SO2 Na H R2 S 2: 48% 2: 43% 2: 0%
R1
DMSO, 50°C, 8h Ph 3: 67% Ph 3: 0%
Ph 3: 29%
R2
Plausible mechanism
O O O O
Nu Nu IArX -ArI Nu
S S R I X
-X
R R
S Ar
NO2 NO2 5 6
93% 82%
Nu
O O O Nu
O or
R Nu or
S S O R
R
O C-H carbene insertion
NO2 1,2-rearrangement
87% 83% (five membered ring formation)
Scheme 2 Palladium-catalyzed cross-coupling reaction of sodium sulfinates

Scheme 5 Reaction of alkyl sulfinates with alkynyl(aryl)iodonium salts.
with alkynes.
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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2.2 Sulfonylation of alkynes with sulfonylhydrazides pentyl substituted phenylacetylenes. Heteroaryl acetylenes, such as
It is important to note that sulfonyl radicals generated from various pyridyl and thiophenyl acetylenes were also compatible substrates
sulfonyl compounds, such as sulfonyl halides,
14
selenides,
15 and delivered the corresponding (E)-β-iodovinylsulfones. However,
cyanides, 16
azides,17
and sodium sulfinates, 18
etc. Recently, the yield diminished markedly when aliphatic alkyne was used. A
sulfonyl radical addition to aryl acetylenes and subsequent trapping
Taniguchi has demonstrated that sulfonyl radicals can be generated
19 of the C-centered alkenyl radicals intermediate with I2 or iodine free
from the corresponding hydrazine compounds. In 2013, Xu and
20 radicals, was believed to be the mechanism (Scheme 7). It is also
co-workers combined sulfonylhydrazides with FeCl3 or FeBr3,
possible that the reaction might occur through addition of
which was used as the Cl and Br source, to allow chlorosulfonylation
arenesulphonyl iodides to aryl acetylenes.
or bromosulfonylation of alkynes (scheme 6). Generally,
bromosulfonylation and chlorosulfonylation exhibited similarly
I 2 (0.5 equiv)
I
reactivity, both giving moderate yields. A mechanism involving R TsNHNH 2
TBHP (2.0 equiv)

MeCN, 80°C, 1h R Ts
radical pathway was given (Scheme 6). Firstly, sulfonyl radicals were
generated from sulfonylhydrazides under the irritation of the tert- I I I
butoxyl and tert-butylperoxy radicals. Then, addition of sulfonyl Cl
Ts Ts Ts
radical to the Fe-coordinated alkynes was subsequently occurred. F3C
At last, the (E)-β-halovinylsulfones were afforded through reductive 93% CF3
75%
94%
elimination of Fe(IV) intermediate to the Fe(II) catalyst. I
I
I I
Ts
Ts
FeCl3 6H2 O Ts Ts
R or FeBr3 (2 equiv) O
X C 5H 11 N
TBHP (2 equiv)
SO2 Ar 84% 56% 83% 22%
ArSO2 NHNH2 CH 3 CN, 80°C, 3h R
Proposed mechanism
O O
Ar
O t-BuOOH Ar S
Ph S Ts ArSO 2NHNH 2 Ar SO2 Ar
Cl O 11
7
X X
X = Cl, 78% X = Cl, 70% I2 I I
I2
X = Br, 40% X = Br, 49%
S X O I
Ts Ar
Ar S I
Ar SO2Ar
X Ts O
X = Cl, 49% X = Cl, 36% 12
X = Br, 42% X = Br, 36%
Scheme 7 TBHP mediated reaction of sulfonylhydrazides and iodine with
Proposed mechanism aryl acetylenes.
t-BuOOH Fe(II) Fe(III)(OH) t -BuO

In 2015, a new approach to the selective synthesis of (E)-
-H2 O
t -BuOOH Fe(III)(OH) Fe(II) t-BuOO vinylsulfones via a Fe/Cu co-catalyzed sulfonylation of
O O
phenylacetylene with sulfonylhydrazides was demonstrated by Mao
t -BuO 22
ArSO2NHNH 2 Ar S
Fe(III) X
Ar S X and co-workers (Scheme 8). Several alkyl and halo substituted aryl
t-BuOO alkynes and heterocyclic alkynes, furnished the reactions smoothly
O O
7 8 affording the desired products in moderate to good yields, with
R SO2Ar
exclusively E isomers obtained (Scheme 8). And the reaction was
Fe(III)X3 believed to mechanistically proceed via sulfonyl radical
R R X 3(VI)Fe
10 addition/reductive elimination pathway.
Fe(III)X3
9 Fe(II)X 2 copper acrylate (20 mol%)
FeCl2 4H2O (15 mol%) Ts
R TsNHNH 2 R
R SO2Ar DTBP, 100°C, 12h
X Ts
Ts Ts
Scheme 6 Chlorosulfonylation or bromosulfonylation of alkynes with
H 3C(H 2C)4
sulfonylhydrazides. TBHP, tert-butyl hydroperoxide.
81% 71% 56%
Interestingly, Li and co-workers21 reported an efficient and simple Ts Ts Ts
protocol for the preparation of (E)-β-iodovinylsulfones by TBHP Cl F

N
mediated reaction of aryl acetylenes with sulfonylhydrazides and 84% 76% 62%
iodine (Scheme 7). The reactions of various substituted
Scheme 8 Fe/Cu co-catalyzed sulfonylation of phenylacetylene with
phenylacetylenes with TsNHNH2 were examined. Good to excellent
sulfonylhydrazides. DTBP, di-tert-butyl peroxide.
yields were observed with halogen, trifluoromethyl, methyl, and n-

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Very recently, the hydrosulfonylation of terminal alkynes with regenerated Cu(II) catalyst.
sulfonylhydrazides reaction using copper(I) as the catalyst was also
utilized to achieve the construction of (E)-vinyl sulfone scaffolds23 O
R
O O BrettPhosAu(TA)]OTf (5 mol%)
(Scheme 9). This hydrosulfonylation proceeds smoothly in S
OH R'
Ga(OTf)3 (10 mol%) O S
moderate yields, and this transformation features a good tolerance R

dry DCE, RT-45°C, Ar R'
of substrates including aliphatic sulfonylhydrazides. A plausible O O

Ph Ph O Ph O Ph
reaction mechanism involving sulfonyl radical is also given, which is O S O S O S O S
22
similar to the literature reported by Mao. Cl
MeO F3 C
CuI (10 mol%) O 91% 69% 50% 62%
O S R
2,2'-bpy (10 mol%)
RSO2 NHNH2 Ar O Ph O O Ph O
p-MeC6H 4 Ph
DMF, air, 100°C, 18h
Ar O S O S O S O S

O O Cl O
O S O CF3 O
O S O S 70%
O S 74% 71% 78%
Scheme 10 Gold-catalyzed sulfonylation of terminal alkynes with arylsulfinic

acids. BrettPhos, 2-(dicyclohexylphosphino)-3,6-dimethoxy-2’,4’,6’-
77% 35% Br 51%
35%
O O O
triisopropyl-1,1’-biphenyl. TA, 1H-benzotriazole, DCE, 1,2-dichloroethane,
O S O
O S O S O S Tf, trifluoromethanesulfonyl.
O O O
S Cu(OAc)2 (5 mol%) O
OH S
50% 41% 60% 53% R R' R
DME, 60°C, N2
R'
Scheme 9 Copper-catalyzed hydrosulfonylation of terminal alkynes with O O O
O O O
sulfonylhydrazides. 2,2’-bpy, 2,2’-bipyridine. S S S CF3
2.3 Sulfonylation of alkynes with arylsulfinic acids 94% 71% 90%

O O O
O O
Sulfonyl radicals could be generated from the corresponding sulfinic S O
S S
acids and were involved in the procedures for the oxidative

difunctionalization of alkenes and alkynes, which was disclosed N
S
24 75% 91% 64%
recently by Lei’ group. Under transition-metal or metal-free
Postulated reaction pathway
conditions, sulfonyl radical addition to alkynes or alkenes were both CuII(OAc)2 O O
O O CuII(OAc)2
exclusively given the trans-configured β-substituted vinyl sulfones, R3 SO2 R3 S
S R3 S
25 R3 OH
whose behavior is similar to the anti-Markovnikov addition. But, HOAc 13 CuIOAc 14
O
14'
O
there are little literature reporting the efficient synthesis of a-

R1 R2
substituted vinyl sulfone scaffolds. And these previous methods
26 HOAc CuI OAc
suffer from poor a/β regioselectivity and limited substrate scope. H SO2 R3 AcOCuII SO2 R3 SO2 R 3
27
In 2014, Shi and co-workers reported that a-substituted vinyl R1 R2 R1 R2
R1 R2
CuII(OAc)2
sulfones were generally synthesized via gold-catalyzed Markovnikov 16 15
addition of arylsulfinic acids to alkynes (Scheme 10). Various Scheme 11 Copper-catalyzed sulfonylation of alkynes with arylsulfinic acids.
aromatic alkynes, heteroaromatic alkynes and aliphatic alkynes
O
were tested and gave the corresponding products in modest to O O R1
S Ar S R
I2 (50 mol%)
good yields. The reaction tolerated both electron-withdrawing and R
OH
O
DME, 100°C, 12-24h I R2
electron-donating groups. Ar
28
In 2013, Wang and co-workers reported an efficient approach
MeO O
for the construction of vinyl sulfone scaffolds via copper-catalyzed O CF3
O Ph S
direct sulfonylation of arylsulfinic acids with alkynes (Scheme 11). In S S Ph
S Ph O
O
general, aromatic or heteroaromatic alkynes, and arylsulfinic acids O I
I
I
with electron-donating or withdrawing groups were tolerated in 88% 62% 77%
this process to afford the corresponding products. The proposed

O
O
mechanism of the reaction was shown in Scheme 11. Firstly, O S Ph
O
EtO S Ph
sulfonyl radical could be generated from arylsulfinic acid under Ph S O
O
II I
I
oxidation by Cu via the single electron transfer (SET) process. O
I
Subsequently, vinyl radical was formed via the selective addition of 74% 36% 12%
I
sulfonyl radical to alkyne, which interacted with Cu species to Scheme 12 Difunctionalization of alkynes with arylsulfinic acids and
obtain vinyl copper(II) complexes. Finally, the vinyl sulfones were molecular iodine. DME, dimethylether.
given after protonation of vinyl copper(II) complexes and

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29
Very recently, Wang’s group also presented a protocol of reaction of vinylindium, derived from terminal alkynes via
direct difunctionalization of alkynes with arylsulfinic acids and hydroindation, with sulfonyl chlorides in the presence of Ag2O
molecular iodine for the preparing (E)-β-iodovinyl sulfones provides access to (E)-vinyl sulfones (scheme 15). A reasonable
(Scheme 12). Without metal catalyst or additives, various explanation is that Ag2O seems to promote the leave of chlorine as
substituted (E)-β-iodovinyl sulfones in moderate to good yields anion, while an attack by vinylindium is at the same time made in
with excellent stereo- and regioselectivities were provided. the opposite direction, thus leading to favorable generation of vinyl
And a radical process was postulated in this reaction system, sulfones (scheme 15).
which sulfonyl radical species was easily generated from O
arylsulfinic acids under air. O O
HPO(OEt)2 (1.1 equiv) S
R1 R2 S
CuSO 4 5H2O (25 mol%)
R1 R2
2.4 Sulfonylation of alkynes with DMSO
TFA (20 mol%), 120°C, 10h
O O O

Dimethyl sulfoxide (DMSO) has been widely used not only as a S S S
O O O
solvent but also as a reagent in chemistry. While methyl sulfonyl
n-C4 H 9
radicals generated from DMSO in organic synthesis are rarely 68% 90% 85%
30 31
reported. In 2014, Loh and co-workers demonstrated that DMSO O O O
S
was activated in a new catalytic system which involves copper, S S
O O O
oxygen and HPO(OEt)2 to afford a methyl sulfonyl radical that can N
S
functionalize alkynes for synthesis of (E)-vinyl methyl sulfones 75% 73% 82%
(Scheme 13). The proposed reaction mechanism is given in scheme Scheme 14 Copper-catalyzed sulfonylation of alkynes with DMSO. TFA,
13. Initially, methyl sulfonyl radical was probably generated and trifluoroacetic acid.
subsequently reacted with alkynes to form vinyl radical. After
hydrogen atom transfer, only E isomer vinyl methyl sulfones was
32 1) InCl3, NaBH 4, CH 3CN, N 2, -15°C
detected (Scheme 13). Very recently, Zhao and co-workers also R
R
SO2R'
2) R'SO2Cl, Ag2O, rt
developed a novel and practical CuSO4·5H2O catalyzed H-
phosphonate promoted synthesis of (E)-vinyl alkylsulfones from Ts Ts O O
S Ts
alkynes and DMSO (Scheme 14).
80% 36% 77% 0%
O
O
R2 CuBr (0.1 equiv) S
O
Plausible mechanism O
HPO(OEt)2 (3.0 equiv) O
R1 S R2
O2 (1 atm), H 2O, 120°C R1 InCl3 S
In R'SO 2Cl Cl
R Ag
NaBH 4 R Ag 2O R'
H
R1 = H, 85% O
R1 = 4-F, 82% O O 20 In
O O R1 = 4-F, 82% S R Ag
S R1 = 4-t-Bu, 79%
SO 2R' 21
R1 R1 = 4-F, 82% AgCl AgO In R
R1 = 4-OMe, 80%
R1 = 4-NO 2, 63% 77%
R1 = 2-Me, 75% Scheme 15 Reaction of vinylindium with sulfonyl chlorides.
R1 = 2,4,5-tr i-Me, 54%
Ph
O O O O O
Pd(OAc)2 (10 mol%) S
S S O O O O
DMEDA (20 mol%)
O S S O Y
S R Y t -BuOK (2 equiv)
68% Ph Ph O
75% DMF/MeCN, 120°C, 24h
R
Proposed mechanism
O Ph Ph Ph
O H O O O
CuL n/O2 Ph S
S S
S S O O O
O Ph SO 2Me N
N N O
18 O O O
17 Ph
65% 79% 71%
Ph H atom abstraction Ph H Ph Ph
Ph O O
O S S
SO2Me S O O
SO2 Me O
19 S N NH
N
O Ph O Ph
Scheme 13 Copper-catalyzed sulfonylation of alkynes with DMSO. O Ph
50% trace
74%
Scheme 16 Pd-catalyzed sulfonylation of alkynes with 1,2-

2.5 Sulfonylation of alkynes with other sulfone sources
bis(phenylsulfonyl)ethane. (DMEDA, N’,N’-dimethylethane-1,2-diamine)
(sulfonyl chlorides, 1,2-bis(phenylsulfonyl)ethane, thiols
34
and t-butylsulfinamide) In 2011, Li and co-workers reported that 1,2-
bis(phenylsulfonyl)ethane can act as the sulfone resource, which
In 2010, Deng and Zou33 illustrated the first nucleophilic generated phenylsulfonyl intermediates in situ for the conjugate
substitution reaction of organoindium with sulfonyl chlorides. This addition to the electron-deficient alkynes leading to the

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corresponding (E)-vinyl sulfones (Scheme 16). The procedure predominant products. The optimized conditions were also
underwent the C-S bond cleavage and conjugate addition in the consistent with aliphatic alkynes. The plausible mechanism via
Pd(OAc)2/DMEDA catalytic system. The results showed that a wide addition/radical trapping/oxidation process was discussed by the
variety of 3-arylpropiolamides, and several N-substituents, either authors.
alkyl or aryl groups, took place smoothly under the standard Despite the remarkable improvement in vinyl sulfone synthesis,
conditions. And the reaction was believed to mechanistically the discovery of diverse sulfone sources is still highly desired. In
36
proceed via insertion of Pd(0) into 1,2-bis- 2015, Chen and Zhao’group disclosed that (E)-vinyl sulfone
(phenylsulfonyl)ethane/complexation with an alkyne/regioselective scaffolds could be obtained from t-butylsulfinamide and alkynes in
additions/reductive elimination pathway. the CuSO4-phosphorous acid catalytic system (Scheme 18). It is the
first example of the use of t-butylsulfinamide as a sulfur source to
O
H 2O2 (0.2 mL)
O
S R1 prepare vinyl sulfones. The reaction mechanism is not fully
NH4Cl (1 equiv)
R 1 SH R2
understood. While the cleavage of the N–S bond of t-

THF, 50°C, 48h R2
butylsulfinamide, which was catalyzed by CuSO4·5H2O-phosphorous
O O O O acid catalytic system, was the key step for this transformation.
S S
O
F F
98% 82% 3. Sulfonylation of alkenes
O O O O
S S 3.1 Sulfonylation of alkenes with sodium sulfinates
F During the past two decades, the versatility of hypervalent iodine
86% 90% reagents in organic synthesis is well recognized owing to their mild,
Scheme 17 Metal-free hydrothiolation of alkynes. highly selective, and environmentally benign properties.37
Currently, both iodine(V) and iodine(III) reagents are widely used in
O 38
O
H3 PO3 (2.0 equiv) organic synthesis. One of the most important and commercially
S CuSO 4 5H 2O (20 mol%) S
R1 H2N
TFA (2.0 equiv), DMF, 100°C, 12h
R1 available iodine(III) reagents is (diacetoxyiodo)benzene [PhI(OAc)2],
O
which is easy to handle and comparable in reactivity to heavy metal
O O O containing reagents. In 2010, an efficient protocol of synthesis of
S S
S
O vinyl sulfones under PhI(OAc)2/KI-mediated addition of aryl
O O 39
sulfinates to alkenes was described by Kuhakarn and co-workers
C 2H5 F
81% 79% 55% (Scheme 19). A variety of aliphatic alkenes, including those
O O containing an oxygen atom, a bromine atom, an aldehyde function
O
S S
S and a 1,3-dioxane moiety, gave the corresponding products. And
N O O
O
S the optimized reaction conditions were also proved to be suitable
51% 70% 69% for a range of alkyl ester derivatives. The reaction was proposed to
Plausible mechanism
mechanistically proceed via β-iodosulfonylation/dehydroiodination
H O pathway (Scheme 19).
O
S
H P OH O R1
O O
OH S H PhI(OAc)2 (1.5 equiv)
S O SO2Na
H2N II KI (1.0 equiv)
Cu 22 R Ts
H2O R
OH MeCN, rt, 1h
R1 H 3 PO 4
O
O Ts O Ts
O P OH H O Ts Br
2 7
OH S H
S R1
R1 O 75% 80%
O O H 80%
H
H P OH O O
O Ts
23 OH 7 O Ts t-BuO Ts
O
Scheme 18 Synthesis of (E)-vinyl sulfones from alkynes and t- 81% 81% 62%
butylsulfinamide.
Plausible mechanistic pathway
O Ts
It is an attractive protocol for the preparation of vinyl sulfone PhI(OAc) 2 R
scaffolds through direct addition–oxidation of thiols with alkynes. In ONa
-PhI
KI -HI
35 -KOAc
2012, Zhu and co-workers disclosed a metal-free, highly selective SO2Na
O I
O R
approach to (E)-vinyl sulfones from hydrothiolation of alkynes S I Ts
R
(Scheme 17). It was the first example for the construction of vinyl O I
O
24 26
sulfone scaffolds in one-pot by direct addition–oxidation of thiols 25
with alkynes. Aromatic alkynes bearing substituents such as methyl, Scheme 19 Synthesis of (E)-vinyl sulfones from alkyenes and sodium
methoxy, and fluoro proceeded smoothly to afford (E)-isomeric sulfinates catalyzed by PhI(OAc)2.

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40
In 2011, Das and co-workers synthesized vinyl sulfones by Electrosynthesis could effectively avoid the use of hazardous or
treatment of alkenes with sodium arene sulfinates using potassium toxic oxidants and achieve oxidation and reduction reactions in mild
iodide and sodium periodate in the presence of a catalytic amount electron-transfer conditions, demonstrating its advantages and
of acetic acid at room temperature, and the applicability of both environment friendly characteristics. In 2015, Yuan and co-
42
aromatic and aliphatic alkenes are the notable advantages of this workers reported a convenient and efficient electrochemical
method (scheme 20). Mechanistically, NaIO4 oxidizes KI to liberate route for the synthesis of vinyl sulfones from sodium sulfinates and
I2, which converts ArSO2Na into ArSO2I. In the presence of acetic olefins (Scheme 22). A plausible reaction mechanism for the
acid, the liberation of I2 was found to be rapid. Next, the reaction of electrochemical synthesis of vinyl sulfones was also proposed
ArSO2I with an olefin produces the β-iodosulfone. Finally, (Scheme 22). At the inert graphite anode, iodine ions are oxidized
－－
spontaneous elimination of HI from this β-iodosulfone furnishes the to I2 (2I → I2＋2e ). The sulfinate sodium salt reacts with I2 to
corresponding vinyl sulfones (scheme 20). generate sulfonyl iodide intermediate, which is decomposed to give
a sulfonyl radical. Then, the addition of the sulfonyl radical to

KI (10 mol%)
NaIO4 (10 mol%)
olefins affords carbon-centered radical intermediate, followed by
R ArSO2Na SO2Ar the reaction with iodine radical or I2 to form iodio-intermediate,
AcOH (cat), M eCN, rt R
which undergoes HI eliminating to provide the target product.
Cl
SO2 Ph SO2 Ph SO2 Ph
Ts
NHCbz NaI-DMSO C
Cl Ar RSO 2Na Ni SO2R
Ar
89% 87% 92% 95% rt
Plausible mechanism O O O O O O
S S S
KI NaIO4 I2
Cl
81% 87% 78%
I2 ArSO2 Na ArSO2 I
I Proposed reaction mechanism
-HI SO2Ar
R ArSO2I SO2Ar R
R Cathode Anode
O
27 RSO 2Na -e -
S I 1/2 I 2 I2
Ar
1/2 H 2 O
Scheme 20 Synthesis of (E)-vinyl sulfones from alkyenes and sodium 12
sulfinates catalyzed by KI and NaIO4.

O
Nickel S I Graphite
+ e- Ar
O
7 Ar
11
Subsequently, Kuhakarn and co-workers reported an improved HI
Ar
SO 2R
I- 28
and convenient experimental procedure to synthesize vinyl sulfones I
I
from alkenes by molecular iodine–mediated one-pot SO 2R
SO 2R Ar
Ar
iodosulfonation followed by base-induced dehydroiodination 29
reaction (Scheme 21a). Very recently, a molecular iodine-mediated
reaction of preparing vinyl sulfone scaffolds from sodium sulfinates Scheme 22 Electrosynthesis of vinyl sulfones from olefins and sodium
and alkenes using environmentally benign water as the solvent sulfinates.
under room temperature was also demonstrated by Wang and
41 Using green light, the organic dye eosin Y as photocatalyst and
Yang (Scheme 21b).
43
nitrobenzene as the terminal oxidant, König and co-workers
I2 (3.0 equiv)
NaOAc (1.5 equiv) recently demonstrated the visible light-mediated synthesis of vinyl
R ArSO2 Na SO2Ar
(a) R
MeCN, reflux, 1h sulfone scaffolds from olefins with aryl sulfinates (Scheme 23). The
O O
reaction allows the conversion of a variety of aryl sulfinates and
Ts
O2N S
Ts 1,2-dihydronaphthalene. Styrene derivatives with electron-donating
O and electron-withdrawing substituents in the para position, and the
55%
93% 35% bulky naphthalene moiety were also tolerated and afforded the
O Ts
Ts products. The mechanism of the photocatalytic vinyl sulfone
Ts synthesis was proposed that the photoreaction proceeds via a
58% 70% 55% radical pathway and oxidative quenching cycle (Scheme 23).
I2 (1.5 equiv)
(b) Ar Ar'SO 2Na Ar
SO 2Ar' 3.2 Sulfonylation of alkenes with sulfonylhydrazides
H 2 O, rt, 2h
Iodine, a nonmetallic element, has diverse valence states as well as
O O O O O O
S S S moderate redox potentials, which make it possible for serving as an
efficient catalyst instead of transition metals in many organic
F Cl 44 45
91% reactions. Recently, Lei’ group reported their progress in the
88% 96%
iodide-catalysed radical alkenylation of sulfonyl hydrazides with
Scheme 21 Synthesis of (E)-vinyl sulfones from alkyenes and sodium simple alkenes, and demonstrated that iodine behaves as a metal in
sulfinates catalyzed by I2. the alkenyl functionality recovery of carbon radicals. (Scheme 24).

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In the initial cycle, iodide was oxidized under acidic conditions, In 2014, a methodology of preparation of vinyl sulfones by means
I
which can promote sulfonyl radical generated from sulfonyl of Cu -catalyzed aerobic oxidative N-S bond cleavage of sulfonyl
hydrazides through dehydrogenation procedure. Subsequently, hydrazides, followed by cross-coupling reaction with alkenes to
46
catalytic HI elimination was proceeded via alkenylation of sulfonyl construct Csp2-S bonds was reported by Jiang and co-workers
radicals from various sulfonyl hydrazides, which is similar to the β- (Scheme 25). The use of aromatic and heteroaromatic alkenes as
hydride elimination of transition metals (Scheme 24). well as naphthalene led to the cross-coupling products. However,
the steric effect was critical for the reactivity. While aliphatic and
aromatic sulfonyl hydrazides were shown to be suitable cross-
eosin Y (10 mol%)
R'
green LED (535 nm) R coupling partners for this oxidative transformation. The mechanism
ArSO2Na ArO 2S
R PhNO 2 (1.0 equiv) R' for this copper-catalyzed aerobic oxidative cross-coupling reaction
DMF/H 2O (3:1), 40°C, 18h

was proposed (Scheme 25). Initially, sulfonyl hydrazides were
O O O O

S S oxidatively decomposed under copper and air, with the release of
O
N2 and H2O. Subsequently, active sulfonyl cuprate was formed,
F
54% 46% which reacts further with alkenes to afford the corresponding
O O
O O
S
products. The authors also speculated that DMSO might serve as a
S
co-oxidant in this transformation.
O
51% 19%
Proposed mechanism
O O CuCl (10 mol%) O O
R'
O S LiBr (30 mol%) S
O R NHNH2 R' R R'
R DMSO, 100°C, air, 12h
S S
Ar O Ar
O O O O O
30 31 S S
ArSO 2Na R NO 2
ArO2S 72% 87%
PC R'
Ph NO2
32 O O O O
O O
PC* S S N
Ph NO2 S
CN
33 S
Ph NH 2 88% 88%
visible light PC 54%
R
ArO2S
R' Proposed mechanism air
O O O
Scheme 23 Visible light-mediated synthesis of vinyl sulfones from olefins O O R S S R S
S R NHNH 2
and sodium sulfinates. PC, photocatalyst. R R' L n CuI X O
37
N 2, H 2O
KI (40 mol%)
O O O O
TBHP (2.0 equiv)
S S
R NHNH2 R' R R'
DMSO / H2 O = 1:1
25-30°C, 10h RSO2 Cu I XLn (RSO2)2 CuIII XLn
39 38
F O O O O O2, DMSO
Br S S
R'
H 2O, MeSMe
76% 79%
Ts Br
Scheme 25 Copper-catalyzed oxidative sulfonations of alkenes.
Ts O
O
79% 69%
Proposed mechanism
3.3 Sulfonylation of alkenes with sulfonyl chlorides
O O O O
R
S
R' S Recently, visible-light photoredox catalysis has emerged as a
TBHP R NHNH2
HI
powerful tool to promote useful redox transformations. In 2013,
N 2 + t-BuOH 47
t -BuO H2O Zhang and Yu developed the direct sulfonation of enamides with
TBHP sulfonyl chlorides to generate vinyl sulfones instead of the addition
O O I H 2O O
S 1/2 I2
R S
of sulfonyl chlorides to C=C bonds to generate a-chlorosulfones
R R'
36
34 O
(scheme 26). Direct C- 1 H functionalizations of enamides or
O O enecarbamates under the optimized conditions proceeded with a
S R'
R R' wide scope of substrates and remarkable selectivity to give
35 functionalized vinyl sulfones with good to excellent yields. They
Scheme 24 Iodide catalyzed oxidative radical alkenylation for the synthesis
envisaged that sulfonyl radical, which could be generated from
of alkenyl sulfones.
sulfonyl chloride under photocatalysis conditions, could add to
enamide to give the amido radical. The resulting amido radical

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could be easily oxidized to furnish the N-acyliminium. Upon and hydroxyl radicals with the assistance of the iodide anion.
deprotonation of N-acyliminium and tautomerization, the Secondly, the decomposition of the diazonium salts in the presence
amidovinyl sulfone could be formed as the final product (scheme of t-BuO－forms the phenyl radical. Subsequently the addition of
26). DABSO affords sulfonyl radical. Then, addition of sulfonyl radical to
I2 formed Sulfonyl halides. Sulfonyl halides easily generate
R2
O
Ir(ppy)2(dtbbpy)PF 6 (0.1 equiv)
corresponding sulfonyl radicals and cause atom transfer radical
R2 O N
RSO2 Cl R1 N SO2 R additions to multiple bonds. Alternatively, addition of sulfonyl
NaH 2 PO 4 (3 equiv) R1
blue LED (3 W), MeCN radical to alkenes forms carbon-centered radical. The radical reacts
hv [Ir]
deprotonation with in situ generated iodine to generate β-iodosulfone. Finally,
R2 R2
O [O] O elimination of HI similar to the β-hydride elimination forms
N N
RSO2
products to finish the catalytic cycle (Scheme 28).
40 R1 SHO 2Ar R1 SO 2Ar

41 42

O TBAI (10 mol%) O
CF3 O S O O
O TBHP (2.0 equiv)
S O O O S R1
S S S R 1 N2 BF4 R2 DABCO (SO2 )2 R2
N MeCN, 80°C, Ar, 12h O
O N O N O O N
N
O O
O
92%
98% 95% 98%
F S NO2 S
S Ph
Ph Ph O
O O O
O O
O CF3 O O 84%
O O CF3 S CF3 80% 78%
S S O
S O O
O
O O S Ph
O N N O NH N S Ph
S
Cbz Ph O O
71% O N O
65% 79% 86%
88% 83% 71%
Scheme 26 Vsible-light photoredox-catalyzed sulfonation of alkenes. Proposed mechanism 1/2 I2
I TBHP OH t-BuO
PhN2
3.4 Sulfonylation of alkenes with DMSO O
48 S R1 O
In 2015, Yuan and Li provided a novel method via ammonium R2 R2 I2 DABSO
O Ph S I PhSO2 Ph
iodide-induced sulfonylation of alkenes to afford vinyl sulfone
43 O
scaffolds utilizing DMSO as the versatile sulfur source (Scheme 27). HI DABSO
O O
Aromatic and heteroaromatic olefins proceeded smoothly to afford I
I2
R2
S R1 S R1 PhSO2
the target products. Also, interminal alkene and conjugated diene R2 R2
O O 44
were productive, while allylbenzene failed to give the 46 45
corresponding product. And the reaction was believed to Scheme 28 Iodide-catalyzed radical alkenylation using aryl diazonium salts,
mechanistically proceed via radical pathway. terminal alkenes and DABSO. DABCO (1,4-diazabicyclo[2.2.2]octane), TABI
(tetrabutylammonium iodide), DABSO (DABCO·SO2).
O
O NH 4I (4.0 equiv)
R S H 2O S
130°C R
O
O O O
4. Decarboxylative sulfonylation of α,β-
S
S
F O
O N
S
unsaturated carboxylic acids
O S O
F O
88% 89% 87% 4.1 Decarboxylative sulfonylation of α,β-unsaturated

O O O carboxylic acids with sodium sulfinates
S S Ph S
Ph Ph In the past decades, decarboxylative coupling reactions have been a
O O O
86% 46% 0% prominent research topic because they provided straightforward
Scheme 27 Ammonium iodide-induced sulfonylation of alkenes. and efficient pathways to the formation of carbon−carbon and
carbon−heteroatom bonds under relatively mild conditions.51
Recently, a few approaches were described for converting α,β-
3.5 Sulfonylation of alkenes with SO2 unsaturated carboxylic acids to vinyl sulfones. In 2014, Pd-catalyzed
decarboxylative cross-coupling reaction of cinnamic acid with arene
Recently, Willis developed a new convenient reagent DABSO
(DABCO·SO2, the combination of DABCO and sulfur dioxide), which sulfinic acid sodium salts for preparing vinyl sulfone scaffolds was
52
can serve as a surrogate of SO2 for the in situ formation of sulfinate reported by Tan and co-workers (Scheme 29). The reaction was
49
salts in the synthesis of sulfonamides and sulfamides. In 2015, found to tolerate both electron withdrawing and electron donating
50
Feng and co-workers reported an efficient one-pot, three- groups, affording various vinyl sulfones. Two possible reaction
component synthesis of vinyl sulfones via iodide-catalyzed radical mechanisms for this coupling were also proposed (Scheme 29).
53
alkenylation using aryl diazonium salts, terminal alkenes and DABSO In 2014, Guo and co-workers reported a Cu(II)-catalyzed
(Scheme 28). The control experiments suggested a possible radical decarboxylative sulfonylation of alkenyl carboxylic acids with
mechanism. First, TBHP decomposes to generate the tert-butoxyl sodium sulfinates using air as the oxidant (Scheme 30). It is the first

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aerobic decarboxylative sulfonylation of alkenyl carboxylic acids ligand-promoted decarboxylative coupling of sodium aryl sulfinates
utilizing sodium sulfinates as the sulfur source without any silver with α,β-unsaturated acids (Scheme 31a). This decarboxylative
additives for stereoselective synthesis of (E)-alkenyl sulfones. The radical coupling reaction proceeded exclusively to afford the (E)-
mechanistic study indicates that the initial sulfonyl cation addition isomer using a catalytic amount of Cu(ClO4)2·6H2O, 1,10-
and the following decarboxylation processes are involved in this phenanthroline as a ligand, and TBHP in decane as an oxidant.
transformation (Scheme 30). Interestingly, using DMSO as the oxidant, a tandem cross-
decarboxylative/coupling reaction for the preparation of vinyl
COOH SO2 Na
Pd(OAc)2 (10 mol%)
O
S
sulfone scaffolds from cinnamic acid and sodium sulfinates under
dppb (10 mol%) 55
R1 R2
AgCO 3 (2.0 equiv)
R1 O R2
transition-metal-free conditions was reported by Jiang’s group
DMF, 75°C
(Scheme 31b). The mechanism study of the reaction indicated that
O
O
O
S
O S a radical pathway could be involved.
S 56
O
O O Very recently, Mao and Shi reported an iodine-promoted

F NO 2 66%
61%
65% decarboxylative C-S bond formation through cinnamic acids
O
O O
S F S and sodium benzene sulfinates in the absence of metal
S
O O O
catalyst (Scheme 32a). In 2015, an efficient and green protocol
O2 N 56%
53% 57%
for the preparation of (E)-vinyl sulfones via iodine-promoted
Proposed mechanism decarboxylative cross-coupling reactions of sodium sulfinates
O
O COOH
S Ph
with cinnamic acids using water as the solvent was developed
by Yuan and co-workers57 (Scheme 32b). Kuhakarn’group58
S Ph AgCO 3 O
O Pd(OAc)2
Pd(OAc)2
AgCO 3 Pd(0) also demonstrated the synthesis of (E)-vinyl sulfones via
Pd(0)
PhI(OAc)2 mediated decarboxylative sulfonylation strategy
O
O
O Pd S Ph (Scheme 32c). A wide range of functionalities both in the
Pd S Ph O Pd OAc O
O 51 aromatic and heteroaromatic unsaturated carboxylic acids and
47
49
SO2 Na the sodium aryl sulfinates are tolerated with these reaction
Ph
Ph
SO2Na
conditions. And the preliminary study on these reaction
O Pd OAc
O mechanisms also implies that these reactions are probably
O Pd S Ph
O 50 proceeding through a radical pathway.
48
Scheme 29 Pd-catalyzed decarboxylative sulfonylation of α,β-unsaturated COOH Cu(ClO 4 . 6H 2O (20 mol%)

O
SO2Na S
TBHP in decane (3 equiv)
carboxylic acids with sodium sulfinates. dppb (1,4- (a) R 1 R2
1,10-phenanthroline (20 mol%)
R1 O R2
bis(diphenylphosphino)butane). CH 3CN, 110°C, 20h
O O O
O S Cl S S Cl
O O O
O S
CuO (20 mol%) O O O
COOH SO2Na S R 52% 33%
Ar 54%
R KI (1.5 equiv) Ar
O
DMSO, air, 100°C O
K 2CO 3 (50 mol%)
COOH S R1
O (b) R1 SO 2Na R2 R2
NO2 O O DMSO, 100°C, 10h
O
S Ph S Ph S Cl
Ph
O Cl O
O O O O
O
N S S S
HO 64% S S
72% 34% O O
O O
O O O 85%
85% 83% 73%
S Ph S Ph S
O O O
N
O Scheme 31 Decarboxylative sulfonylation of α,β-unsaturated carboxylic acids
67% 57% 33%
with sodium sulfinates.
Proposed mechanism
O O
O O2 O O
Cu(II), O2 or DMSO Ph S
PhSO2 Ph S Ph S COOH SO2 Na S
[I]
O
52 52' O 53 O R1 R2 R1 R2
Cu(II)O COOCuII
COOH Ar (a) Mao and Shi's condition:
Ar -H2 O 54 O
O
I2 (2 equiv), TBHP (2 equiv),Toluene, 90°C, 12h
I O
O I S Ph (b) Yuan's condition:
O Ar
-Cu II S Ph
S R Ar
Ar COOCuII I2 (1 equiv), K2CO 3 (1 equiv), H 2O, 60°C, 10h
O -CO 2 COOCu II
55 (c) Kuhakarn's condition:
56
O2 PhI(OAc)2 (2 equiv), DMF, 100°C, 10-30min
CuI CuII
Scheme 30 Cu-catalyzed decarboxylative sulfonylation of α,β-unsaturated Scheme 32 I2 or PhI(OAc)2-promoted decarboxylative sulfonylation of α,β-
carboxylic acids with sodium sulfinates. unsaturated carboxylic acids with sodium sulfinates.
Subsequently, Prabhu and co-workers presented a efficient

54 Recently, Wang and Zha59 developed an electrochemical
II
method for the preparing vinyl sulfones via Cu -catalyzed and decarboxylative sulfono functionalization protocol for preparing (E)-

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vinyl sulfones directly from cinnamic acids and sodium sulfinates triple bond resulting from the deprotonation of
with high regioselectivity at room temperature (scheme 33). In light phenylpropiolic acid in the presence of basic sodium sulfinate.
of the experiments, a possible sulphonyl radical-based pathway was An anionic was readily produced after the removal of one
also discussed by the authors. molecule of carbon dioxide followed by the abstraction of a
hydrogen radical from phosphoric acid. With the assistance of
phosphoric acid, the desired product was obtained.
R4 n-Bu 4NClO 4, HOAc R4
R1
R1
COOH R2 SO 2Na
MeCN/H 2O
SO2R2 4.2 Decarboxylative sulfonylation of α,β-unsaturated
I = 20 mA, C/Pt
R3 R3 carboxylic acids with sulfonylhydrazides
SO 2Ph SO 2Ph SO 2Ph Arylsulfonyl hydrazides have evolved as excellent synthons in recent
N
years and behave as a source for a sulfur nucleophile or electrophile
O2N 26%
77% 45% depending upon the nature of the reaction conditions. Very

O O O O recently, Singh and co-workers61 reported a novel metal-free
SO 2Ph
S S protocol for room temperature decarboxylative sulfono
O NO2
47%
functionalization using the reaction of sulfonyl hydrazides with
trace 0% cinnamic acids, to provide a range of vinyl sulfone molecules
(Scheme 35). The reaction is presumed to involve a sulfonyl radical,
Scheme 33 Electrochemical decarboxylative coupling between cinnamic which is formed by the sequential N−H abstraction by an iodine
acids and sodium sulfinates. radical generated by the reaction of I2 with TBHP. The resulting
sulfonyl radical subsequently undergoes addition to cinnamate
O
followed by iodine catalyzed decarboxylation to afford (E)-vinyl
H 3 PO 4 (2 equiv) S R1
R1 SO 2Na R2 COOH
DMSO, 80°C, air, 12h
R2 sulfones (Scheme 35).
O
O O O
S Ph S Ph S CF3
Ph I2 (40 mol%)
O O O DBU (1.5 equiv)
NC 64% COOH TBHP (2.5 equiv) SO 2R
87% 90% Ar R SO2 NHNH2 Ar
O CH 3CN/H 2O (3:1)
O O
rt, air, 1h
S S
S Ph Ph
Ph O
O O O O O
82% 85% O
64% S S
S Ph
O
Plausible Mechanism O
O O O2N
DMSO O
R1 SO 2Na Ph S Ph S 74% 75% 68%
O
O
57 57' Plausible Mechanism SO2R
O Ar
I2 / TBHP
R2 COOH R1 SO 2H R2 COO R SO2 NHNH2 R S
58 O I2
61
O
COOH DBU COO COO
O O S R1 Ar Ar Ar
S R1 H 3PO4 H3 PO4 R2 SO 2R
R2 S R1 O 62 63
R2
O O O O
Scheme 35 I2-catalyzed decarboxylative coupling between cinnamic acid and
60 59
sulfonyl hydrazides. DBU, 1,8-diazabicyclo[5,4,0]undec-7-ene.
Scheme 34 Decarboxylative coupling between phenylpropiolic acid and
sodium sulfinates. 22
Interestingly, Mao and Zhang established a new approach to the
selective synthesis of (E)-vinyl sulfones via a Fe/Cu co-catalyzed
In 2015, Mao and Zhang60 reported a novel phosphoric acid-
sulfonylation of arylpropiolic acids with sulfonyl hydrazides (Scheme
mediated synthesis of vinyl sulfones through decarboxylative 23
36a). Subsequently, Yang and Wu developed direct
coupling reactions of sodium sulfinates with phenylpropiolic
decarboxylative hydrosulfonylation of arylpropiolic acids with
acids (Scheme 34). A broad range of substrates, including both
sulfonylhydrazides via copper-catalyzed under base-free conditions
substituted propiolic acids and sodium sulfinates, were
to obtain (E)-vinyl sulfones (Scheme 36b). This reaction features a
tolerated with this protocol under optimal conditions, and a
simple catalytic system and good tolerance of substrates including
variety of vinyl sulfone products were obtained in moderate to
aliphatic sulfonylhydrazides. Both the mechanism of the above two
excellent yields. The plausible mechanism was also proposed
reactions are presumed to involve a sulfonyl radical, which is
(Scheme 34). An oxygen-centered radical was initially
generated by Fe/Cu and DTBP or CuI and O2. And arylpropiolic acids
generated through the oxidation of sodium sulfinate by DMSO
can be transformed to alkynylcopper(I) by releasing CO2. The
upon heating, which could be resonance-stabilized with a
resulting sulfonyl radical subsequently undergoes addition to
sulfonyl radical. Next, carbon-centered intermediate was
alkynylcopper(I) to afford (E)-vinyl sulfones.
formed through the trans addition of sulfonyl radical to the

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COOH O O n-Bu 4NBr (5 mol%)

copper acrylate (20 mol%)
SO 2NHNH 2
FeCl2 4H2 O (15 mol%)
S HCl (30 mol%)
X R2 SO 2Na SO2 R2
(a) R 1 R2 R1 R2 R1 R1
DTBP (3 equiv) H2 O, 100°C, 10h
DMSO, 100°C, air, 12h
O O O O
Cl O O O O O O
S S O2N S HO S
S
NO2 O
30% 66% 42%
96% 59%
O O O O
CuI (10 mol%)
O O S O O S
2,2'-bpy (10 mol%) S Ph S Ph
(b) R SO2 NHNH2 Ar COOH Ar R Ph
DMF, 100°C, air, 18h S
61% 53% 51%
O O O O O O
S S S
Plausible mechanism
CF3 O
36% 72% 55%
Br

Scheme 36 Decarboxylative coupling between arylpropiolic acid and sulfonyl Br SO2Ar
hydrazides. SO2 Ar
Ar SO2 Na 64 NaBr
4.3 Decarboxylative sulfonylation of α,β-unsaturated

carboxylic acids with arylsulfinic acids Scheme 38 Transition-metal-free coupling of vinyl halides with sodium
Very recently, encouraged by Mao and Zhang’ work,
22 sulfinates.
62
Kuhakarn and co-workers reported Na2CO3-promoted
decarboxylative sulfonylation of arylpropiolic acids with Epoxides, three-membered heterocycles, which can be used as
arylsulfinic acids in the absence of a transition metal catalyst starting materials as well as intermediates in order to carry out
(scheme 37). This simple and environmentally benign various synthetic transformations, possess some advantages, such
65
transformation offers an alternative approach and allows for as ease of preparation, ready accessibility in enantioriched forms
easy and rapid synthesis of (E)-vinyl sulfones. The preliminary and high reactivity towards a large variety of reagents, in particular
66
study on the reaction mechanisms implies that the reaction is nucleophiles. Recently, using water as the reaction solvent, an
probably proceeding through a radical pathway. efficient regioselective preparation of vinyl sulfones catalysed by
Lithium bromide from sodium sulfinates and terminal epoxides in a
67
one-pot procedure was disclosed by Yadav and co-workers. And
Na2CO3 (1 equiv)
Ar COOH Ar' SO2H Ar
SO2Ar' this reaction gave two regioisomers (linear and branched vinyl
DMF-H2O
sulfones) in most cases (Scheme 39). The plausible mechanism
O O O O might undergoes through regioselective nucleophilic epoxide
S S
opening with the sulfinate group of sodium sulfinates and
NO 2 O 2N Cl dehydrative β-elimination of β-hydroxy sulfones affording vinyl
57% 88%
sulfones and liberating Lithium bromide to complete the catalytic
O O O O cycle .
Br S S
R2 R2
O O
59% 50% O SO2 Na LiBr (10 mol%) O O
R2 S O S
R1 H2 O, 80-90°C O
Scheme 37 Decarboxylative coupling between arylpropiolic acid and R1 R1
arylsulfonic acid.
Ph Ph
O O
S O S Ph Ph
Ts Ts O O O
S O S
O
Ph Ph Cl Cl
5. Sulfonylation of vinyl halides, terminal epoxides, 75% 13%
0% 75%
64% 17%
oxime acetates and β-nitrostyrenes Plausible mechanism
In recent years, more efficient methods using transition-metal O R2

O
R1
catalysts, such as Pd or Cu, for the cross-coupling of sulfinate salts S
O
LiBr
with allenyl boronic acids, vinyl bromides, or vinyl triflates for R1

-H 2 O
preparing vinyl sulfones were reported.63 But there are still filled
Li Br
with great challenges for the use of toxic metals or organic solvents. R1
Li Br O
OH O S
In 2013, a transition-metal-free route to (E)-vinyl sulfones from the O
S R1 NaO
coupling of sodium sulfinates with vinyl halides in water was R2 O H 65 R2
H 2O
64
reported by Chen and Yu (Scheme 38). The tentative mechanism 66
-NaOH
might undergoe through nucleophile addition of sodium sulfinate to Scheme 39 Synthesis of vinyl sulfones from terminal epoxides and sodium
phenylvinyl bromide and elimination of the bromine anion giving sulfinates.
the desired product (Scheme 38).

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DOI: 10.1039/C6RA10731A
II
In 2014, a procedure involving Cu -catalyzed N-O bond cleavage, tosyl group for the first time (Scheme 42). They postulated that the
activation of a vinyl sp2 C-H bond, and C-S bond formation for reaction of tosylhydrazone with CNBr−TBAB to form vinyl sulfones
synthesis of β-sulfonylvinylamines from sodium sulfinates and proceeds through radical mechanism (Scheme 42). The tosyl group
68
oxime acetates was reported by Jiang and co-workers (Scheme migration in these reactions has been further confirmed by
II I
40). One proposed mechanism is might undergo the Cu /Cu performing a mixed reaction of two sulfonyl hydrazine derivatives
catalytic cycle through a single electron transfer process. Another with CNBr−TBAB under the optimal conditions, which yielded a
possible mechanism might involve a key organocopperIII mixture of vinyl sulfone products.
II III
intermediate, which was proposed to occur via a Cu /Cu catalytic
cycle. H
N Ts CNBr (1.1 equiv)
N
TBAB (2.5 equiv) Ts
OAc NH2
N Cu(OAc)2 (10 mol%) R1

SO2 Na Ts R1 dioxane, 100°, 8-12h R2
toluene, N 2 , 100°C, 6h Ar R2
Ar

Ts Ts Ts
NH2 Cl NH2
NH2
Ts Ts Ph Ph
Ts
93% 69% 84%
Ts
75% 72%
92% F Ts Ts
Br NH2 NH2
Ts MeO
Ts
52% 54%
72%
82% 90%
Plausible Reaction Mechanism
Scheme 40 Synthesis of vinyl sulfones from oxime acetates and sodium H
sulfinates. N Ts Ts
N Ts N2
Br
N N
CNBr
Ar
Very recently, an efficient silver-catalyzed one-pot protocol for Ar base R
R Ar 68
the highly stereoselective synthesis of (E)-vinyl sulfones by Br
Br R
67
denitrative radical cross-coupling of readily available β- Br
Ts
nitrostyrenes and sodium sulfinates at room temperature under Ar R
or Ar Ts Ar
mild reaction conditions was investigated by Yadav and co- Ts R
workers69 (scheme 41). This is the first report on the facile R = Me, Ph R=H 69
1,2-sulf one migration no rearrangment
formation of C(sp2)–S bonds leading to vinyl sulfones. And the
reaction involves a radical addition/elimination pathway for the Scheme 42 Synthesis of vinyl sulfones from tosylhydrazone.
formation of the product.
H
N Ts
AgNO 3 (20 mol%) N Cu(OAc)2 H 2 O (15 mol%) Ts
NO2 SO2 R2 Ar
R1 R2 SO 2Na R1 R
K 2 S2O 8 (2 equiv) Ar xylene, 90-140°, Ar, 2-3h R
DMF, rt, N 2
Ts Ts
Br Ts
O O O O O O
Ph
S S S F
Ph Ph Ph
86% 81% 93%
90% 80% 73% O
O O O
Ts
O O O O O O S S
S
Ph Ph
S S S S Ph
Ph Ph Ph
S F
83% 81% 94% 95%
85% 0%
Plausible Mechanism
Scheme 41 Synthesis of vinyl sulfones from β-nitrostyrenes and sodium H
H H N Ts
sulfinates. N Ts N Ts CuII CuIII
N HN HN
R
R R R Ar
Ar Ar Ar
71
Cu II NH2 NH 2 Ts
70
6. Decomposition of tosylhydrazones H OH H 2O Cu II
Ts tr ans-elimination R R
Ar Ar Ar
In recent years, N-tosylhydrazones, derived from simple ketones, R Ts II Ts
H 2O Cu
which were utilized as the precursors of diazo compounds, have 73 72
broad applications in constructing complex molecules by transition-
70
metal-catalyzed or metal-free cross-coupling reactions. In 2014, Scheme 43 Copper-catalyzed synthesis of vinyl sulfones from
71
Prabhu and co-workers revealed a novel reaction of tosylhydrazone.
tosylhydrazone with CNBr and aliphatic quarternary ammonium
72
salts for preparing vinyl sufones and witnessed the migration of a Very recently, wang and co-workers described the first

PleaseRSC
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DOI: 10.1039/C6RA10731A
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elimination of H2O to afford vinyl sulfone. 3 (a) H. Kumamoto, K. Deguchi, T. Wagata, Y. Furuya, Y.

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RSC Advances Page 16 of 16
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DOI: 10.1039/C6RA10731A
Recent advances in the synthesis of vinyl sulfones
Yuyu Fang, Zaigang Luo* and Xuemei Xu
COOH
R1 X
R1
"S"

R1 "S"
"S"
O Ts
O
"S" S R Decomposition NH
N
R1 R1 R1
"S" "S"
R1
OAc
"S" N
COOH R1
R1 O
"S" sulf one sources
RSO 2Na RSO 2NHNH 2 RSO 2H RSH DMSO.....
This review focus on recent achievements in vinyl sulfones synthesis and the mechanisms of the reactions are also
discussed.

Fang 2016

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This is an Accepted Manuscript, which has been through the

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Recent advances in the synthesis of vinyl sulfones

Yuyu Fang, Zaigang Luo* and Xuemei Xu

RSC Advances Accepted Manuscript

have been predominantly utilized, probably due to their good

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bromoalkenyl sulfones are possible to convert into various alkenyl O O O O

Scheme 2 Palladium-catalyzed cross-coupling reaction of sodium sulfinates

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t-BuOOH Fe(II) Fe(III)(OH) t -BuO

Interestingly, Li and co-workers21 reported an efficient and simple Ts Ts Ts

protocol for the preparation of (E)-β-iodovinylsulfones by TBHP Cl F

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moderate yields, and this transformation features a good tolerance R

of substrates including aliphatic sulfonylhydrazides. A plausible O O

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Scheme 10 Gold-catalyzed sulfonylation of terminal alkynes with arylsulfinic

2.3 Sulfonylation of alkynes with arylsulfinic acids 94% 71% 90%

acids and were involved in the procedures for the oxidative

there are little literature reporting the efficient synthesis of a-

this process to afford the corresponding products. The proposed

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TFA (20 mol%), 120°C, 10h

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65% 79% 71%

Scheme 16 Pd-catalyzed sulfonylation of alkynes with 1,2-

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RSC Advances Accepted Manuscript

sulfinates catalyzed by KI and NaIO4.

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DMF/H 2O (3:1), 40°C, 18h

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40 R1 SHO 2Ar R1 SO 2Ar

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Scheme 26 Vsible-light photoredox-catalyzed sulfonation of alkenes. Proposed mechanism 1/2 I2

88% 89% 87% 4.1 Decarboxylative sulfonylation of α,β-unsaturated

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Scheme 29 Pd-catalyzed decarboxylative sulfonylation of α,β-unsaturated COOH Cu(ClO 4 . 6H 2O (20 mol%)

bis(diphenylphosphino)butane). CH 3CN, 110°C, 20h

Subsequently, Prabhu and co-workers presented a efficient

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COOH O O n-Bu 4NBr (5 mol%)

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4.3 Decarboxylative sulfonylation of α,β-unsaturated

In recent years, more efficient methods using transition-metal O R2

with allenyl boronic acids, vinyl bromides, or vinyl triflates for R1

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N Cu(OAc)2 (10 mol%) R1

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reaction with water to regenerate the copper catalyst and trans-