A facile sulfenylchlorination of alkenes with Me2SO/(COCl)2

Article abstract of DOI:10.1080/00397911.2018.1560473

The sulfenylchlorination of a series of alkenes is investigated by using the combined reagent of dimethyl sulfoxide and oxalyl chloride. The corresponding β-chloro sulfides were obtained in mediate to good yields. Most of the terminal alkenes give the Mar

Full text of DOI:10.1080/00397911.2018.1560473

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: https://www.tandfonline.com/loi/lsyc20
A facile sulfenylchlorination of alkenes with
Me2SO/(COCl)2
Liyuan Lan, Yang Gao, Rui Ding, Ting Zhang, Yongguo Liu, Baoguo Sun &
Hongyu Tian
To cite this article: Liyuan Lan, Yang Gao, Rui Ding, Ting Zhang, Yongguo Liu, Baoguo Sun
& Hongyu Tian (2019): A facile sulfenylchlorination of alkenes with Me2SO/(COCl)2, Synthetic
Communications, DOI: 10.1080/00397911.2018.1560473
To link to this article: https://doi.org/10.1080/00397911.2018.1560473
View supplementary material
Published online: 23 Jan 2019.
Submit your article to this journal
Article views: 5
View Crossmark data
Full Terms & Conditions of access and use can be found at
https://www.tandfonline.com/action/journalInformation?journalCode=lsyc20

R
SYNTHETIC COMMUNICATIONSV
https://doi.org/10.1080/00397911.2018.1560473
A facile sulfenylchlorination of alkenes with Me2SO/(COCl)2
Liyuan Lan, Yang Gao, Rui Ding, Ting Zhang, Yongguo Liu, Baoguo Sun, and
Hongyu Tian
Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing Key Laboratory of
Flavor Chemistry, Beijing Technology and Business University, Beijing, China
ABSTRACT
ARTICLE HISTORY
Received 1 October 2018
The sulfenylchlorination of a series of alkenes is investigated by
using the combined reagent of dimethyl sulfoxide and oxalyl chlor-
ide. The corresponding b-chloro sulfides were obtained in mediate
to good yields. Most of the terminal alkenes give the Markovnikov
adducts mainly and the sulfenylchlorination of cyclic alkenes is
stereospecific to produce the adducts with trans configuration.
Methanesulfenyl chloride is supposed to be the real species for sulfe-
nylchlorination.
KEYWORDS
Sulfenylchlorination;
alkenes; dimethyl sulfoxide;
oxalyl chloride;
methanesulfenyl chloride
GRAPHICAL ABSTRACT
Introduction
It is a very important process in organic synthesis that the electrophilic additions across
carbon-carbon double bonds introduce two different vicinal functional groups simultan-
eously to alkene substrates.[1–6] The sulfenylchlorination of alkenes has been paid a lot
of attention due to the great flexibility of b-chloroalkyl sulfides for structural elabor-
ation. The most common approach for the sulfenylchlorination is by the addition of
reagents containing an S-Cl bond to alkenes. Various organic sulfonyl chlorides add to
alkenes catalyzed by copper(I) chloride[7] or ruthenium(II) complexes[8–11] affording
b-chlorinated sulfones, and unsaturated sulfonyl chlorides undergo an intramolecular
addition to give cyclized products.[12,13] Meanwhile, organic sulfenyl chlorides are also
widely used for the sulfenylchlorination, such as bezenesulfenyl chloride, methanesulfenyl
chloride,[14] and electron-poor trifluoromethanesulfenyl chloride.[15] The additions
between chloro(pentafluoro)-k6-sulfane and various alkenes have been investigated for
the products with the potential pharmacological activities.[16,17] In addition, several com-
bined reagents have been developed to achieve this process, such as dimethyl sulfoxide
activated by phenyl dichlorophosphate or phosphorus oxychloride,[18] trimethylchloro- or
CONTACT Hongyu Tian
tianhy@btbu.edu.cn
Beijing Advanced Innovation Center for Food Nutrition and Human
Health, Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University, Beijing 100048, China.
Supplemental data for this article can be accessed on the publisher’s website.
ß 2019 Taylor & Francis Group, LLC

2
L. LAN ET AL.
Scheme 1. Sulfenylchlorination of alkenes with DMSO-(COCl)2.
trimethylbromosilane-dimethyl sulfoxide[19,20] and dimethyl sulfide/sulfuryl chloride/
dimethyl sulfoxide.[21] A quite new combination for sulfenylchlorination of alkenes is
dimethyl sulfoxide/HCl/DMPU (1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone) reported
by Xu et. al.[22]
The combination of dimethyl sulfoxide and oxalyl chloride has been used widely in
the oxidation of primary and secondary alcohols[23] since it was developed by Swern
et al.[24] We have developed several applications of the combined reagents of R2SO (R =
Me or Ph) and (COX)2 (X = Cl or Br) for other transformations, such as sulfenyllacto-
nization[25] and chlorolactonization of alkenoic acids,[26] bromination of alkenes,
alkynes and ketones,[27] preparation of a,b-unsaturated c-lactones[28] and sulfenyletheri-
fication[29] in our recent work. For sulfenyllactonization, methanesulfenyꢀl chloride was
proposed as the real species for the reaction, which was generated at 0 C via DMSO
attack on the dimethylchlorosulfonium salt derived from the reaction of (COCl)2 with
DMSO.[25] It is conceivable that the combination of dimethyl sulfoxide and oxalyl
chloride can also serve as a sulfenylchlorination reagent for alkenes. Herein, we report
our results about the reactions of a series of alkenes with dimethyl sulfoxide and oxalyl
chloride (Scheme 1).
Results and discussion
A total of twelve alkenes are investigated, including 5 terminal alkenes, 3 cyclic alkenes,
3 allylic alcohols, and 1 allyl trans-2-butenoate. The obtained results are shown in
Table 1. 1-Decene 1a was sulfenylchlorinated with DMSO/(COCl)2 to produce a
Markovnikov adduct 1-methylthio-2-chlorodecane 2a mainly in 87% yield, which
contained about 7% of the anti-Markovnikov adduct 1-chloro-2-methylthiodecane
(Entry 1). In the case of allylbenzene 1b, 1-methylthio-2-chloro-3-phenylpropane 2b
was obtained in 90% yield also containing a certain amount of anti-Markovnikov adduct
(11%) (Entry 2). 3,3-Dimethyl-1-butene 1c was converted into a single Markovnikov
adduct, 1-methylthio-2-chloro-3,3-dimethylbutane 2c in 92% yield (Entry 3). Likewise,
the sulfenylchlorination of 1-cyclohexylethene 1d also afforded a single Markovnikov
adduct, 1-chloro-1-cyclohexyl-2-methylhtioethane 2d in 88% yield (Entry 4). In contrast,
the reaction of styrene 1e underwent with relatively poor regioselectivity (Entry 5). The
crude product was a mixture of Markovnikov and anti-Markovnikov adducts 2e with a
1
ratio of 3/1 based on the H NMR spectrum. After purification on silica gel column,
the corresponding hydrolyzed product 1-hydroxy-1-phenyl-2-methylthioethane 3a was
obtained in 87% yield.
For cylcohexene 1f, 1-chloro-2-methylthiocyclohexane 2f was generated in 96% yield
(Entry 6), which was determined to be trans configuration based on the multiplicities
of the protons attached to the C-1 and C-2 positions in the 1H NMR spectrum.

R
SYNTHETIC COMMUNICATIONSV
3
Table 1. The reaction results of alkenes with DMSO/(COCl)2.
Entry Substrate
Product
Reaction Yield
timea
(%)
87b
1
5 h
2a
1a
2
5 h
90b
92
2b
1b
3
12 h
10 h
2c
1c
4
88
2d
1d
5
2 h
90c
87d
2e
1e
3a
6
1h
96c
93d
91
2f
1f
3b
7
3 h
2 h
2g
1g
8
86c
81d
2h
1h
3c

4
L. LAN ET AL.
Table 1. Continued.
9
5 h
5 h
5 h
65e
2i
2i
2j
2j
2k
1i
10
68e
1j
11
33
41
80
1k
2k
12
5 h
2l
1l
(a) The experiments of entries 1–8 were carried out in CH2Cl2 at 0 ꢀC ꢁ rt, and entries 9 ꢁ 12 in CH3CN at 0–55 ꢀC.
(b) The contents of the anti-Markovnikov adducts based on the 1H NMR data were 7% (Entry 1), 11% (Entry 2), and
33% (Entry 5), respectively. (c) The yield based on GC analysis before purification by column chromatography. (d) The
yield of the product obtained after purification by column chromatography. (e) The yield of the mixture.
1
The stereoselectivity was confirmed further by comparison of the H NMR data with
those of trans-1-chloro-2-methylthiocyclohexane in literature.[20,21] Similar to the prod-
uct 2e, 1-chloro-2-methylthiocyclohexane 2f also hydrolyzed to 1-hydroxy-2-methylthio-
cyclohexane 3b when submitted on silica gel column for purification. The hydrolyzed
product 3b was trans configuration same as 2f. Cylcopentene 1g was transformed to the
corresponding adduct 2g in 91% yield without hydrolysis occurring on silica gel column
(Entry 7). 1-Chloro-2-methylthiocycloheptane 2h was also obtained as the crude prod-
cut when cylcoheptene 1h was treated under the same conditions as above (Entry 8),
which was converted to 1-hydroxy-2-methylthiocycloheptane 3c after purification on sil-
ica gel column. The relative configuration of the products 2g, 2h and 3c was deter-
mined by NOE experiments to be trans.
Three allyl alcohols were also investigated, including trans-2-hexen-1-ol 1i, cis-2-
hexen-1-ol 1j, and 1-hexen-3-ol 1k. No desired product was produced when trans-2-

R
SYNTHETIC COMMUNICATIONSV
5
hexen-1-ol 1i was treated with DMSO/(COCl)2 under the above conditions. When the
reaction was carried out in CH3CN instead of CH2Cl2 and the reaction temperature was
ꢀ
ꢀ
raised to about 55 C from 0 C after the addition of 1i, a mixture of anti-1,3-dichloro-
2-methylthiohexane 2i and syn-1-methylthio-2,3-dichlorohexane 2i0 with a ratio of
about 1/1 was obtained in about 65% yield (Entry 9). Under the same conditions, cis-2-
hexen-1-ol 1j was converted to a mixture of syn-1,3-dichloro-2-methylthiohexane 2j
and anti-1-methylthio-2,3-dichlorohexane 2j0 in 68% yield with a ratio of about 1/4
(Entry 10). It failed to separate two isomers on silica column for these two reactions.
1
However, the H NMR signals in the lower field were apart from each other enough to
be identified with the aid of H–H cosy, C–H cosy, and HMBC. When 1-hexen-3-ol 1k
was treated with DMSO/(COCl)2 under the same conditions, syn- and anti-1-methyl-
thio-2-chloro-3-hexenol (2k and 2k0) were obtained in 33% and 41% yields respectively
(Entry 11). Allyl trans-2-butenoate 1l reacted with DMSO/(COCl)2 to give 20-methyl-
thio-30-chloropropyl trans-2-butenoate 2l in 80% yield (Entry 12).
Among the five terminal alkenes under investigation, two substrates 1c and 1d gave
single Markovnikov adducts, whereas the sulfenylchlorination of the other three sub-
strates 1a, 1b, and 1e afforded mixtures of Markovnikov and anti-Markovnikov adducts.
The Markovnikov adducts predominated in all cases. The additions to the substrates 1a
and 1b presented similar regioselectivities with ratios of 13/1 and 8/1, respectively,
whereas the substrate 1e showed the poorest regioselectivity with a ratio of 3/1. It was
reported that anti-Markovnikov products were kinectically favored at low temperature
for steric reasons when the sulfenyl chlorides were used as sulfenylchlorination reagents
directly.[14] Whereas, the anti-Markovnikov products were susceptible to isomerize to
the thermodynamically more stable Markovnikov products at ambient temperature.
However, styrene reacted with methanesulfenyl chloride to give the Markovnikov prod-
uct preferentially with a ratio of 49/1, which was interpreted due to some carbonium
ion character in the transition state.[14] In contrast, the reaction of styrene 1e in our
work didn’t show the same preference for the Markovnikov product as literature,[14]
which indicated that the carbonium ion character of the episulfonium ion intermediate
in the transition state was not very significant in our reaction system. This regioselectiv-
ity for the Markovnikov product is consistent with that of the combined reagents, tri-
methylchloro- or trimethylbromosilane-dimethyl sulfoxide[20] and dimethyl sulfide/
sulfuryl chloride/dimethyl sulfoxide[21] developed by Bellesia et. al. However, styrene
was not examined in these two literatures.[20,21] Another combined reagent, dimethyl
sulfoxide activated by phenyl dichlorophosphate or phosphorus oxychloride was
reported to convert styrene into 1,2-dimethylthio-1-phenylethane abnormally instead of
the sulfenylchlorination product.[18]
These results can be interpreted by the involvement of methanesulfenyl chloride,
which is generated via DMSO attack on the chlorosulfonium intermediate as proposed
in our previous work.[25] The electrophilic addition of methanesulfenyl chloride to the
C = C bond of alkene produces an episulfonium ion intermediate, which is then
attacked by a chloride ion to afford the corresponding sulfenylchlorination product
(Scheme 2). The intervention of the episulfonium ion intermediate can also be specu-
lated from the facts that the sulfenylchlorination of cyclic alkenes 1f–h is stereospecific
to afford the products with trans configuration.

6
L. LAN ET AL.
Scheme 2. Proposed mechanism of sulfenylchlorination of alkenes with DMSO/(COCl)2.
Scheme 3. The hydrolysis of b-chloro sulfides on silica gel column.
Three sulfenylchlorination products 2e, 2f, and 2h were observed labile to hydrolyze
on silica gel column. As mentioned above, the product 2e is a mixture of Markovnikov
and anti-Markovnikov adducts. Both adducts were converted to one single product
1-hydroxy-1-phenyl-2-methylthioethane 3a (Entry 5), which should be due to the neigh-
boring group effect of methylthio group (Scheme 3). Likewise, trans-1-chloro-2-methyl-
thiocyclohexane 2f and trans-1-chloro-2-methylthiocycloheptane 2h were transformed
to trans-1-hydroxy-2-methylthiocyclohexane 3b and trans-1-hydroxy-2-methylthiocyclo-
heptane 3c on silica gel column respectively (Entries 6 and 8). In order to confirm the
hydrolyzed product, 3b was acylated with Ac2O in pyridine and 1-acetoxy-2-methylthio-
cyclohexane 4 was obtained successfully. Both 3b and 4 were supposed to be trans con-
figuration according to the multiplicities of the protons attached to the C-1 and C-2
1
positions in the H NMR spectra. Moreover, the NMR data of 3b and 4 were in consist-
ent with those with trans configuration in the literatures.[30,31] These results were also
consistent with the involvement of the neighboring group effect of methylthio group
(Scheme 3). In Xu’s work,[22] the sulfenylchlorinated product was also reported to be
labile to hydrolyze during work up when styrene was treated with DMSO/HCl/DMPU.
However, the sulfenylchlorinated products 2e, 2f, and 2h were observed to be stable
during work up and even could stand in atmosphere for several days without any
hydrolysis occurring in our present work. The hydrolysis of these products should be

R
SYNTHETIC COMMUNICATIONSV
7
Scheme 4. The possible mechanism of sulfenylchlorination of trans- and cis-2-hexen-1-ol.
due to the participation of silica gel. This kind of decomposition of b-chloro sulfide
promoted by silica gel has been reported before for b,b0-dichloro sulfides.[32]
It is interesting that both trans-2-hexen-1-ol 1i and cis-2-hexen-1-ol 1j produced a
mixture of 1,3-dichloro-2-methylthiohexane and 1-methylthio-2,3-dichlorohexane but
with opposite configuration and different ratios (Entries 9 and 10). The possible mech-
anism for the formation of 1,3-dichloro-2-methylthiohexane and 1-methylthio-2,3-
dichlorohexane was proposed as shown in Scheme 4. 2-Hexen-1-ols were first converted
to 2-hexenyl chlorides by the chlorodimethylsulfonium salt. Although the hydroxy
group was not replaced by chloride in our previous work of sulfenyletherification of
unsaturated alcohols,[29] the allyl alcohols were reported to be transformed to the corre-
sponding allyl halides with chloro- or bromodimethylsulfonium salt.[33] The obtained 2-
hexenyl chlorides then reacted with methanesulfenyl chloride via an episulfonium ion
intermediate to give anti- or syn-1,3-dichloro-2-methylthiohexane (2i or 2j), of which
methylthio group and the chloro on the carbon 1 swapped via an episulfonium ion to
generate syn- or anti-1-methylthio-2,3-dichlorohexanes (2i0 or 2j0). The addition of
MeSCl to the double bond and the following swap between methylthio group and
chloro on the carbon 1 are stereospecific due to the intervention of episulfonium ions.
Therefore, trans-2-hexen-1-ol 1i afforded a mixture of anti-1,3-dichloro-2-methylthio-
hexane 2i and syn-1-methylthio-2,3-dichlorohexane 2i0 with a ratio of about 1/1. In
contrast, cis-2-hexen-1-ol 1j produced a mixture of syn-1,3-dichloro-2-methylthiohexane
2j and anti-1-methylthio-2,3-dichlorohexane 2j0 with a ratio of about 1/4. The higher
ratio of anti-1-methylthio-2,3-dichlorohexane 2j0 might be due to the repulsion between
the syn substituents of syn-1,3-dichloro-2-methylthiohexane 2j, which is more favorable
for the occurrence of intramolecular nucleophilic substitution. trans-2-Hexen-1-ol was
reported to be converted to 1,3-dichloro-2-methylthiohexane with excess DMSO/

8
L. LAN ET AL.
TMSCl, but without mention of the relative configuration of the product.[20] The char-
1
acteristic H NMR signals in the lower field of 2i we obtained from trans-2-hexen-1-ol
1i were consistent with the reference data. In contrast, another allyl alcohol 1k pro-
duced two stereoisomers syn- and anti-1-methylthio-2-chloro-3-hexanol 2k and 2k0
with hydroxy group intact (Entry 11). It is unclear why the hydroxy group was not
replaced by chloride in this case. More allyl alcohols will be investigated for chemoselec-
tivity and regioselectivity in our further work.
Ally trans-2-butenoate 1l only produced single isomer product 20-methylthio-30-chlor-
opropyl trans-2-butenoate 2l (Entry 12). It is unexpected that the anti-Markovnikov
adduct was obtained in this case. The double bond conjugate with carbonyl group did
not participate the reaction, which indicates that electron-poor double bond is unreact-
ive toward the electrophilic species CH3SCl in this reaction.
Conclusion
In summary, sulfenylchlorination of the alkenes is carried out with DMSO/(COCl)2 to
afford b-chloro sulfides with preference of Markovnikov adducts in mediate to high
yields. The real species for sulfenylchlorination is supposed to be methanesulfenyl chlor-
ide and the products are generated via episulfonium ion intermediates. The reactions of
allyl alcohols are kind of complicated and the further research is still ongoing in our
lab. This method offers another good alternative for the sulfenylchlorination of alkenes
due to the easy availability of reagents and simple operation.
Experimental
All the alkenes and reagents were purchased from Beijing Bailingwei Science and
Technology Company (Beijing, China). NMR spectra were obtained on a Bruker AV300
or 600 MHz NMR (1H NMR at 300 or 600 MHz, 13C NMR at 75 or 150 MHz) in
CDCl3 using TMS as internal standard. Chemical shifts (d) are given in ppm and cou-
pling constants (J) in Hz.
General reaction procedure of alkenes with dimethyl sulfoxide-oxalyl chloride
To a 50 mL three necked round bottom flask, fitted with a condenser and adapted with
a CaCl2 valve, dimethylsulfoxide (DMSO 1.7 mL, 24 mmol, 2.ꢀ4 equivalents) and CH2Cl2
(10 mL) were poured. The stirred solution was cooled to 0 C and then a solution of
oxalyl chloride (1.0 mL, 12 mmol, 1.2 equivalents) in CH2Cl2 (10 mL) was added drop-
wise from a dropping funnel. After 10 min, a solution of the alkene (10 mmol, 1.0
equivalent) in CH2Cl2 (10 mL) was added. The reaction mixture was then allowed to
warm to room temperature and stirred until TLC showed the reaction completed.
Triethylamine (7.0 mL, 50 mmol, 5.0 equivalents) was added in one portion. After stir-
ring for 10 min, the mixture was successively washed with a saturated aqueous solution
of NH4Cl (30 mL) and brine (2 ꢂ 30 mL). The combined organic extracts were dried
over MgSO4, filtered, and concentrated under reduced pressure. The product was puri-
fied by chromatography on silica gel.

R
SYNTHETIC COMMUNICATIONSV
9
1
1-Methylthio-2-chlorodecane 2a: colorless oil; 1.94 g, 87% yield. H NMR (CDCl3) d
0.88 (t, J = 7.2 Hz, 3H, H-C-10), 1.22–1.46 (m, 11H, H-C-4–9), 1.55 (m, 1H, H0-C-4),
1.68 (m, 1H, H-C-3), 1.97 (m, 1H, H0-C-3), 2.17 (s, 3H, SCH3), 2.81 (dd, J = 13.8, 7.8
Hz, 1H, H-C-1), 2.90 (dd, J = 13.8, 6.0 Hz, 1H, H0-C-1), 4.01 (m, 1H, H-C-2); 13C
NMR (CDCl3) d 14.2 (C-10), 16.6 (SCH3), 22.7 (C-9), 26.3 (C-4), 29.2 (C-5), 29.3 (C-7),
1
29.5 (C-6), 31.9 (C-8), 36.8 (C-3), 42.6 (C-1), 62.0 (C-2). The H NMR data were
matched with those reported in lit.[21]
1-Chloro-2-methylthiocyclohexane 2f: light yellow oil; 1.58 g, 96% yield. 1H
NMR (CDCl3) d 1.30–1.85 (m, 6H, H-C-3–6), 2.17 (s, 3H, SCH3), 2.20–2.35 (m, 2H,
H0-C-3 and H0-C-6), 2.75 (td, J = 7.8, 4.2 Hz, 1H, H-C-2), 4.01 (td, J = 7.8, 3.9 Hz, 1H,
H-C-1); 13C NMR (CDCl3) d 15.0 (SCH3), 23.6 (C-5), 23.9 (C-4), 30.7 (C-3), 34.4
1
(C-6), 52.0 (C-2), 63.5 (C-1). The H NMR data were matched with those reported
in lit.[21]
1-Hydroxy-2-methylthiocyclohexane 3b: colorless oil; 1.36 g, 93% yield. 1H NMR
(CDCl3) d 1.20–1.58 (m, 4H, H-C-4 and H-C-5), 1.65–1.82 (m, 2H, H-C-3 and H-C-6),
2.00–2.22 (m, 2H, H0-C-3 and H0-C-6), 2.07 (s, 3H, SCH3), 2.34 (ddd, J = 12.0, 9.9, 3.9
Hz, 1H, H-C-2), 2.98 (br, 1H, OH), 3.34 (td, J = 9.9, 4.5 Hz, 1H, H-C-1); 13C NMR
(CDCl3) d 11.3 (SCH3), 24.5 (C-5), 26.2 (C-4), 31.5 (C-3), 33.8 (C-6), 53.2 (C-2), 71.0
1
(C-1). The H NMR data were matched with those reported in lit.[31]
Funding
Financial support from the National Key Research and Development Program
(2016YFD0400801), Beijing Postdoctoral Research Foundation (2017-22-011) and the
Importation and Development of High-Caliber Talents Project of Beijing Municipal Institutions
(CIT&TCD20140306) is gratefully acknowledged.
References
[1] Gao, X.; Pan, X.; Gao, J.; Jiang, H.; Yuan, G.; Li, Y. NH4I-Mediated Three-
Component Coupling Reaction: Metal-Free Synthesis of b-Alkoxy Methyl Sulfides from
DMSO, Alcohols, and Styrenes. Org. Lett. 2015, 17, 1038–1041. doi:10.1021/
acs.orglett.5b00170.
[2] Yang, F.-L.; Wang, F.-X.; Wang, T.-T.; Wang, Y.-J.; Tian, S.-K. Iodine-Catalyzed Three-
Component Oxysulfenylation of Alkenes with Sulfonyl Hydrazides and Alcohols. Chem.
Commun. 2014, 50, 2111–2113. doi:10.1039/c3cc48961b.
[3] Muangkaew, C.; Katrun, P.; Kanchanarugee, P.; Pohmakotr, M.; Reutrakul, V.; Soorukram,
D.; Jaipetch, T.; Kuhakarn, C. PhI(OAc)2/KI Mediated 1,2-Acetoxysulfenylation of
Alkenes: Facile Synthesis of b-Acetoxysulfides. Tetrahedron 2013, 69, 8847–8856. doi:
10.1016/j.tet.2013.08.018.
[4] Guan, H.; Wang, H.; Huang, D.; Shi, Y. Enantioselective Oxysulfenylation and
Oxyselenenylation of Olefins Catalyzed by Chiral Brønsted Acids. Tetrahedron 2012, 68,
2728–2735. doi:10.1016/j.tet.2012.01.006.
[5] Denmark, S. E.; Kornfilt, D. J. P.; Vogler, T. Catalytic Asymmetric Thiofunctionalization
of Unactivated Alkenes. J. Am. Chem. Soc. 2011, 133, 15308–15311. doi:10.1021/
ja2064395.
€
[6] Gottlich, R. Synthesis by Addition across C ¼ C Bonds. Sci. Synth. 2007, 35, 189–250.

10
L. LAN ET AL.
[7] da Silva Correa, C. M. M.; Waters, W. A. Electrophilic Character of the p-Toluenesulfonyl
Free Radical. Relative Rates of Its Addition to Substituted Styrenes. J. Chem. Soc., Perkin
Trans. 2 1972, 1575–1577. doi:10.1039/P29720001575.
[8] Kameyama, M.; Kamigata, N.; Kobayashi, N. Asymmetric Addition of Arenesulfonyl
Chlorides to Styrene Catalyzed by a Ruthenium(II) Chiral Phosphine Complex. Chem.
Lett. 1986, 15, 527–528. doi:10.1246/cl.1986.527.
[9] Kameyama, M.; Kamigata, N.; Kobayashi, M. Asymmetric Radical Reaction in the
Coordination Sphere. 2. Asymmetric Addition of Alkane- and Arenesulfonyl Chlorides to
Olefins Catalyzed by a Ruthenium(II)-Phosphine Complex with Chiral Ligands. J. Org.
Chem. 1987, 52, 3312–3316. doi:10.1021/jo00391a025.
[10] Kameyama, M.; Kamigata, N. Asymmetric Radical Reaction in the Coordination Sphere.
III. Asymmetric Addition of Trichloromethanesulfonyl Chloride and Carbon Tetrachloride
to Olefins Catalyzed by a Ruthenium(II) Complex with Chiral Ligand. Bcsj. 1987, 60,
3687–3691. doi:10.1246/bcsj.60.3687.
[11] Kameyama, M.; Kamigata, N. Asymmetric Radical Reaction in the Coordination Sphere.
IV. Ruthenium(II)-Catalyzed Asymmetric Addition of Sulfonyl Chloride to 1-
Phenylpropene. Bcsj. 1989, 62, 648–650. doi:10.1246/bcsj.62.648.
[12] Culshaw, P. N.; Walton, J. C. Regioselectivity in the Formation of Cyclic Sulphones from
4- and 5-Alkenesulphonyl Chlorides. Tetrahedron Lett. 1990, 31, 6433–6436. doi:10.1016/
S0040-4039(00)97084-9.
[13] Culshaw, P. N.; Walton, J. C. Sulfonate Esters as Sources of Sulfonyl Radicals. Ring
Closure Reactions of Alk-4- and -5-Enesulfonyl Radicals. J. Chem. Soc. Perkin. Trans.
1991, 2, 1201–1208.
[14] Mueller, W. H.; Butler, P. E. Factors Influencing the Nature of the Episulfonium Ion in
Sulfenyl Chloride Addition to Terminal Olefins. J. Am. Chem. Soc. 1968, 90, 2075–2081.
doi:10.1021/ja01010a029.
[15] Reetz, M. T.; Seitz, T. Regio- and Stereoselective Carbosulfenylation of Olefins. Angew.
Chem. Int. Ed. Engl. 1987, 26, 1028–1029. doi:10.1002/anie.198710281.
[16] Aït-Mohand, S.; Dolbier, W. R. Jr. New and Convenient Method for Incorporation of
Pentafluorosulfanyl (SF5) Substituents into Aliphatic Organic Compounds. Org. Lett. 2002,
4, 3013–3015. doi:10.1021/ol026483o
[17] Brel, V. K. Synthesis and Epoxidation of 1,3-, 1,4-, and 1,5-Alkadienes with Pentafluoro
k6-Sulfanyl (SF5) Groups. Synthesis 2005, 8, 1245–1250.
[18] Liu, H.-J.; Nyangulu, J. M. A Facile Method for the Synthesis of b-Chloroalkyl Sulfides
Using Dimethyl Sulfoxide Activated by Phenyl Dichlorophosphate or Phosphorus
Oxychloride. Tetrahedron Lett. 1988, 29, 5467–5470. doi:10.1016/S0040-4039(00)80788-1.
[19] Bellesia, F.; Ghelfi, F.; Pagnoni, U. M. Trimethylchlorosilane-Mediated Formation of 2-
Chlorocylcohexyl Sulphides by Sulphoxides and Alkenes. J. Chem. Res. (S). 1987, 24–25.
[20] Bellesia, F.; Ghelfi, F.; Pagnoni, U. M.; Pinetti, A. The Reaction of Trimethylchloro- and
Trimethylbromosilane-Dimethyl Sulphoxide Reagent Systems on Alkenes. Synthesis of 2-
Chloroalkyl and 2-Chlorocylcoalkyl Methyl Sulphides. J. Chem. Res. (S). 1987, 238–239.
[21] Bellesia, F.; Boni, M.; Ghelfi, F.; Pagnoni, U. M.; Pinetti, A. b Chloroalkyl Sulfides from
Me2S/SO2Cl2/Me2SO and Alkenes. Synth. Commun 1992, 22, 1101–1108. doi:10.1080/
00397919208021093.
[22] Ebule, R.; Hammond, G. B.; Xu, B. Metal-Free Chlorothiolation of Alkenes Using HCl
and Sulfoxides. Eur. J. Org. Chem. 2018, 2018, 4705–4708. doi:10.1002/ejoc.201800973
[23] Lee, T. V. Oxidation Adjacent to Oxylgen of Alcohols by Activated DMSO Methods. In
Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 7,
pp 291–303.
[24] Mancuso, A. J.; Huang, S.-L.; Swern, D. Oxidation of Long-Chain and Related Alcohols to
Carbonyls by Dimethyl Sulfoxide "Activated" by Oxalyl Chloride. J. Org. Chem. 1978, 43,
2480–2482. doi:10.1021/jo00406a041

R
SYNTHETIC COMMUNICATIONSV
11
[25] Zhang, T.; Dai, Y.; Cheng, S.; Liu, Y.; Yang, S.; Sun, B.; Tian, H. A Facile Method for the
Sulfenyllactonization of Alkenoic Acids Using Dimethyl Sulfoxide Activated by Oxalyl
Chloride. Synthesis 2017, 49, 1380–1386.
[26] Ding, R.; Lan, L.; Li, S.; Liu, Y.; Yang, S.; Tian, H.; Sun, B. A Novel Method of
Chlorolactonization of Alkenoic Acids Using Diphenyl Sulfoxide/Oxalyl Chloride.
Synthesis 2018, 50, 2555–2566.
[27] Ding, R.; Li, J.; Jiao, W.; Han, M.; Liu, Y.; Tian, H.; Sun, B. A Highly Efficient Method for
the Bromination of Alkenes, Alkynes and Ketones Using Dimethyl Sulfoxide and Oxalyl
Bromide. Synthesis 2018, 50, 4325–4335.
[28] Ding, R.; Li, Y.; Liu, Y.; Sun, B.; Yang, S.; Tian, H. Synthesis of Butenolides by Reactions
of 3-Alkenoic Acids with Diphenyl Sulfoxide/Oxalyl Chloride. Flavour Frag. J. 2018, 33,
397–404. doi:10.1002/ffj.3464
[29] Gao, Y.; Cheng, S.; Zhang, T.; Ding, R.; Liu, Y.; Sun, B.; Tian, H. Dimethyl Sulfoxide/
Oxalyl Chloride: A Useful Reagent for Sulfenyletherification. Synth. Commun. 2018, 48,
2773–2781. 10.1080/00397911.2018.1524495. doi:10.1080/00397911.2018.1524495
€
[30] Honig, H.; Seufer-Wasserthal, P. A General Method for the Separation of Enantiomeric
Trans-2-Substituted Cyclohexanols. Synthesis 1990, 1990, 1137–1140. doi:10.1055/s-1990-
27115.
[31] Takeuchi, H.; Takatori, J.; Iizuka, S. Novel Behavior of Thiiranium Radical Cation
Intermediates. Reactions of Dimethyl Disulfide with Alkenes in the Presence of Pd(OAc)2.
Molecules 2000, 5, 916–926. doi:10.3390/50700916.
[32] Minakata, S.; Mihara, M.; Sugoh, N.; Komatsu, M. Silica Gel-Promoted Synthesis of 1,4-
Oxathiane Derivatives from b,b0-Dichloro Sulfides. Heterocycles 1998, 47, 133–137. doi:
10.3987/COM-97-S(N)50.
[33] Corey, E. J.; Kim, C. U.; Takeda, M. A Method for Selective Conversion of Allylic and
Benzylic Alcohols to Halides under Neutral Conditions. Tetrahedron Lett. 1972, 13,
4339–4342. doi:10.1016/S0040-4039(01)94310-2.