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

Hui Jin; Yiwen Yang; Chunxiang Kuang; Qing Yang

doi:10.1055/s-0031-1289872

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook Linkedin Weibo

Download PDF

Synlett 2011(19): 2886-2890
DOI: 10.1055/s-0031-1289872

LETTER

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

Hui Jin^a, Yiwen Yang^a,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;

Further Information

Publication History

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

Abstract
Full Text
References
Supplementary Material

Buy Article Permissions and Reprints All articles of this category

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

Supporting Information

References and Notes

1a Kondo T, Fukuda T, Wada K, and Koto T. inventors; JP 2008155201.
1b Kuniyasu H. Ogawa A. Miyazaki S. Ryu I. Kambe N. Sonoda N. J. Am. Chem. Soc. 1991, 113: 9796

Search in Google Scholar
1c Mieko A. Masahiko Y. Org. Lett. 2001, 3: 763

Search in Google Scholar
1d Shinichi U. Hideki Y. Hiroshi S. Koichiro O. Org. Lett. 2004, 6: 601

Search in Google Scholar
1e Kolb M. Synthesis 1990, 171
2a Ikeda M, Ishibashi H, Sato T, Kameoka C, and Yoshikawa A. inventors; JP 7061966.
2b Ishibashi H. Kameoka C. Kodama K. Ikeda M. Tetrahedron 1996, 52: 489

Search in Google Scholar
2c Ishibashi H. Kameoka C. Iriyama H. Kodama K. Sato T. Ikeda M. J. Org. Chem. 1995, 60: 1276

Search in Google Scholar
2d Ishibashi H. Kameoka C. Sato T. Ikeda M. Synlett 1994, 445
2e Ishibashi H. Kameoka C. Yoshikawa A. Ueda R. Kodama K. Sato T. Ikeda M. Synlett 1993, 649
3a Mukoyama M, and Kobayashi O. inventors; JP 5086020.
3b Zhao YL. Chen L. Yang SC. Tian C. Liu Q.
J. Org. Chem. 2009, 74: 5622

Search in Google Scholar
3c Thomas AD. Josemin KNN. Asokan CV. Tetrahedron 2004, 60: 5069

Search in Google Scholar
3d Degani I. Dughera S. Fochi R. Serra E. Synthesis 1999, 1200
3e Patro B. Deb B. Ila H. Junjappa H. Tetrahedron 1994, 50: 255

Search in Google Scholar
4a Tanaka M, Kuma S, Funaya M, and Kobayashi S. inventors; WO 03089488.
4b Tanaka M, Kuma S, Funatani M, Kobayashi S, and Kanemura Y. inventors; JP 2001342252.
4c Tanaka M, Kuma S, Funatani M, Kobayashi S, and Kanemura Y. inventors; JP 2001342172.
4d Yamamoto K, Nakano M, and Suzuki M. inventors; WO 9719964.
5a Smyth LA. Matthews TP. Horton PN. Hursthouse MB. Collins I. Tetrahedron 2010, 66: 2843

Search in Google Scholar
5b Yu H. Yu Z. Angew. Chem. Int. Ed. 2009, 48: 2929

Search in Google Scholar
5c Schmidt A. Rahimi A. Gjikaj M. Synthesis 2009, 2371
5d Lubbe M. Klassen R. Trabhardt T. Villinger A. Langer P. Synlett 2008, 2331
5e Hanamoto T. Anno R. Yamada K. Ryu K. Tetrahedron Lett. 2007, 48: 3727

Search in Google Scholar
5f Rao HSP. Sivakumar S. J. Org. Chem. 2006, 71: 8715

Search in Google Scholar
5g Potts KT. Raiford KAG. Keshavarz-K M.
J. Am. Chem. Soc. 1993, 115: 2793

Search in Google Scholar
5h Ogawa T. Hayami K. Suzuki H. Chem. Lett. 1989, 769
6 Cristau HJ. Chabaud B. Labaudiniere R. Christol H.
J. Org. Chem. 1986, 51: 875

Search in Google Scholar
7 Lee P. inventors; WO 2009069888.
8 Murahashi S. Yamamura M. Yanagisawa K. Mita N. Kondo K. J. Org. Chem. 1979, 44: 2408

Search in Google Scholar
9a Bonnafoux L. Colobert F. Leroux FR. Synlett 2010, 2953
9b Wang M. Fu ZQ. Feng H. Dong Y. Liu J. Liu Q. Chem. Commun. 2010, 46: 9061

Search in Google Scholar
9c Pueping M. Parra A. Org. Lett. 2010, 12: 5281

Search in Google Scholar
9d Martinelli F. Palmieri A. Petrini M. Eur. J. Org. Chem. 2010, 5085
9e Zhou HW. Zhu D. Xing YP. Huang HF. Adv. Synth. Catal. 2010, 352: 2127

Search in Google Scholar
9f Rueping M. Stoeckel M. Sugiono E. Theissmann T. Tetrahedron 2010, 66: 6565

Search in Google Scholar
10 Jiang YB. Kuang CX. Yang Q. Tetrahedron 2011, 67: 289

Search in Google Scholar
11 Nakhmanovich AS. Elokhina VN. Glotova TE. Karnaukhova RV. Komarova TN. Sulfur Lett. 1987, 7: 35

Search in Google Scholar
12 Corey EJ. Fuchs PL. Tetrahedron Lett. 1972, 3769

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).