Organic Letters
Letter
methylthiolation of alkenes and alkynes by using CF2HSO2Cl
as a reagent. Reactions of a series of styrene derivatives with
CF2HSO2Cl afforded 6a−6i in good yields (Scheme 5).
Reactions of phenylacetylenes and other alkynes gave products
7a−7j with satisfactory yields. The structure of 7j was
confirmed by single crystal X-ray diffraction analysis. Similar
to the reactions of alkenes with CF3SO2Cl, reactions of styrene
and phenylacetylene derivatives with CF2HSO2Cl gave
Markovnikov products, while other alkenes and alkynes mainly
gave anti-Markovnikov products.
In summary, we have developed a simple and efficient
method for chloro-trifluoromethylthiolation of alkenes and
alkynes using CF3SO2Cl as a bifunctionalization reagent. The
reaction is promoted by the reduction of CF3SO2Cl with PPh3
to form CF3SCl for the electrophilic addition. The hydrolysate
CF3SO3H in the reaction system serves as a catalyst. In addition
to chloro-trifluoromethylthiolation, the method has been
successfully extended for chloro-difluoromethylthiolation
using CF2HSO2Cl. The reactions of styrenes gave regioselective
Markovnikov adducts, while nonstyrene-type alkenes mainly
gave anti-Markovnikov adducts. The highly efficient and
concise nature of the reaction process and good atom economy,
along with the mild conditions employed, are the major
advantages of this new method for direct bifunctional chloro-
fluoromethylthiolation of alkenes and alkynes.
Higher Education Institutions, and the Centre for Green
Chemistry at the University of Massachusetts, Boston and the
Center for Advanced Materials and Technology in Nanjing
University of Science and Technology for financial support.
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ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
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13C, and 19F NMR for products (PDF)
Accession Codes
crystallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Authors
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ORCID
(16) Ferry, A.; Billard, T.; Langlois, B. R.; Bacque,
Int. Ed. 2009, 48, 8551.
́
E. Angew. Chem.,
Author Contributions
§L.J. and T.D. contributed equally.
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M.; Shibata, N. J. Am. Chem. Soc. 2013, 135, 8782. (b) Huang, Z.;
Yang, Y. D.; Tokunaga, E.; Shibata, N. Org. Lett. 2015, 17, 1094.
(c) Arimori, S.; Takada, M.; Shibata, N. Org. Lett. 2015, 17, 1063.
(18) Huang, Z.; Okuyama, K.; Wang, C.; Tokunaga, E.; Li, X.;
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Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We gratefully acknowledge the National Natural Science
Foundation of China (21776138, 21476116), the Fundamental
Research Funds for the Central Universities (30916011102,
30918011314), Qing Lan and Six Talent Peaks in Jiangsu
Province, Priority Academic Program Development of Jiangsu
(20) Yang, Y.; Xu, L.; Yu, S.; Liu, X.; Zhang, Y.; Vicic, D. A. Chem. -
Eur. J. 2016, 22, 858.
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