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Synlett 2011(19): 2886-2890  
DOI: 10.1055/s-0031-1289872
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Room-Temperature and Metal-Free Synthesis of 1,1-Dithio-1-alkenes from 1,1-Dibromo-1-alkenes and Thiols

Hui Jina, Yiwen Yanga,b, Chunxiang Kuang*a, Qing Yang*c
a Department of Chemistry, Tongji University, Siping Road 1239, Shanghai 200092, P. R. of China
Fax: +86(21)65983191; e-Mail: kuangcx@tongji.edu.cn;
b School of Biology and Chemical Engineering, Jiaxing University, Jiaxing 314001, P. R. of China
c Department of Biochemistry, School of Life Sciences, Fudan University, Handan Road 220, Shanghai 200433, P. R. of China
Fax: +86(21)65643446; e-Mail: yangqing68@fudan.edu.cn;
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Publication History

Received 12 August 2011
Publication Date:
11 November 2011 (online)

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Abstract

An efficient metal-free synthesis of 1,1-dithio-1-alkenes from 1,1-dibromo-1-alkenes and thiols using a diazabicycloundecene/dimethyl sulfoxide system was developed. The method was found suitable for various 1,1-dibromo-1-alkenes. The synthesis was completed within 5-15 minutes at room temperature with moderate to excellent yields.

Key words

room temperature - metal-free - 1,1-dithio-1-alkenes - 1,1-dibromo-1-alkenes - thiols

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13

General Procedure for the Synthesis of 3 DMSO (3 mL), 1,1-dibromo-1-alkenes 1 (0.3 mmol), DBU (1.05 mmol), and thiols 2 (0.66 mmol) were placed in a sealed tube. The mixture was stirred at r.t., and the reaction was monitored by TLC. After the reaction was completed, the system was extracted with Et2O (3 × 25 mL). The combined organic layer was washed with H2O and was dried over MgSO4. The solvent was evaporated, and the crude product was purified by silica gel column chromatography to yield 1,1-dithio-1-alkenes 3.
Selected Data[2-(4-Isopropylphenyl)ethene-1,1-diyl]bis( p -tolyl-sulfane) (3a)
Light yellow solid. ¹H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 7.5 Hz, 2 H), 7.39 (d, J = 8.0 Hz, 2 H), 7.23-7.14 (m, 8 H), 6.98 (d, J = 8.0 Hz, 2 H), 2.34 (s, 3 H), 2.22 (s, 3 H).