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
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
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, and Yoshikawa 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, and Kobayashi O. inventors; JP 5086020.
3b Zhao YL.
Chen L.
Yang SC.
Tian C.
Liu Q.
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, 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
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.
5h Ogawa T.
Hayami K.
Suzuki H.
Chem.
Lett.
1989,
769
6 Cristau HJ.
Chabaud B.
Labaudiniere R.
Christol H.
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
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 Et2 O (3 × 25 mL). The combined organic
layer was washed with H2 O 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)
¹ H 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).
