RSS-Feed abonnieren
DOI: 10.1055/s-0031-1289872
Room-Temperature and Metal-Free Synthesis of 1,1-Dithio-1-alkenes from 1,1-Dibromo-1-alkenes and Thiols
Publikationsverlauf
Publikationsdatum:
11. November 2011 (online)
![](https://www.thieme-connect.de/media/synlett/201119/lookinside/thumbnails/10.1055-s-0031-1289872-1.jpg)
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 for this article is available online:
- Supporting Information
-
1a
Kondo T,Fukuda T,Wada K, andKoto T. inventors; JP 2008155201. -
1b
Kuniyasu H.Ogawa A.Miyazaki S.Ryu I.Kambe N.Sonoda N. J. Am. Chem. Soc. 1991, 113: 9796 -
1c
Mieko A.Masahiko Y. Org. Lett. 2001, 3: 763 -
1d
Shinichi U.Hideki Y.Hiroshi S.Koichiro O. Org. Lett. 2004, 6: 601 -
1e
Kolb M. Synthesis 1990, 171 -
2a
Ikeda M,Ishibashi H,Sato T,Kameoka C, andYoshikawa A. inventors; JP 7061966. -
2b
Ishibashi H.Kameoka C.Kodama K.Ikeda M. Tetrahedron 1996, 52: 489 -
2c
Ishibashi H.Kameoka C.Iriyama H.Kodama K.Sato T.Ikeda M. J. Org. Chem. 1995, 60: 1276 -
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, andKobayashi O. inventors; JP 5086020. -
3b
Zhao YL.Chen L.Yang SC.Tian C.Liu Q.
J. Org. Chem. 2009, 74: 5622 -
3c
Thomas AD.Josemin KNN.Asokan CV. Tetrahedron 2004, 60: 5069 -
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 -
4a
Tanaka M,Kuma S,Funaya M, andKobayashi S. inventors; WO 03089488. -
4b
Tanaka M,Kuma S,Funatani M,Kobayashi S, andKanemura Y. inventors; JP 2001342252. -
4c
Tanaka M,Kuma S,Funatani M,Kobayashi S, andKanemura Y. inventors; JP 2001342172. -
4d
Yamamoto K,Nakano M, andSuzuki M. inventors; WO 9719964. -
5a
Smyth LA.Matthews TP.Horton PN.Hursthouse MB.Collins I. Tetrahedron 2010, 66: 2843 -
5b
Yu H.Yu Z. Angew. Chem. Int. Ed. 2009, 48: 2929 -
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 -
5f
Rao HSP.Sivakumar S. J. Org. Chem. 2006, 71: 8715 -
5g
Potts KT.Raiford KAG.Keshavarz-K M.
J. Am. Chem. Soc. 1993, 115: 2793 -
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 - 7
Lee P. inventors; WO 2009069888. - 8
Murahashi S.Yamamura M.Yanagisawa K.Mita N.Kondo K. J. Org. Chem. 1979, 44: 2408 -
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 -
9c
Pueping M.Parra A. Org. Lett. 2010, 12: 5281 -
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 -
9f
Rueping M.Stoeckel M.Sugiono E.Theissmann T. Tetrahedron 2010, 66: 6565 - 10
Jiang YB.Kuang CX.Yang Q. Tetrahedron 2011, 67: 289 - 11
Nakhmanovich AS.Elokhina VN.Glotova TE.Karnaukhova RV.Komarova TN. Sulfur Lett. 1987, 7: 35 - 12
Corey EJ.Fuchs PL. Tetrahedron Lett. 1972, 3769
References and Notes
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).