Unexpected Chemoselective Debromination and Reduction of 1,1-Dibromo-1-alkenes Mediated by Samarium Metal in Methanol

Lei Wang; Pinhua Li; Yuanyuan Xie; Yanbin Ding

doi:10.1055/s-2003-39912

LETTER

Unexpected Chemoselective Debromination and Reduction of 1,1-Dibromo-1-alkenes Mediated by Samarium Metal in Methanol

Lei Wang*^a,b, Pinhua Li^a, Yuanyuan Xie^a, Yanbin Ding^a
Department of Chemistry, Huaibei Coal Teachers College, Huaibei, Anhui 235000, P. R. China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China
Fax: +86(561)3090518; e-Mail: leiwang@hbcnc.edu.cn;

Abstract

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Abstract

An unexpected samarium metal mediated chemoselective debromination and reduction of 1,1-dibromo-1-alkenes in methanol has been developed, which generates vinyl monobromides, alkenes, and alkanes respectively with appropriate molar ratio of samarium to 1,1-dibromo-1-alkene.

Key words

samarium metal - 1,1-dibromo-1-alkenes - debromination - reduction - methanol

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References

1a Girard P. Namy JL. Kagan HB. J. Am. Chem. Soc. 1980, 102: 2693

1b Kagan HB. Namy JL. Tetrahedron 1986, 42: 6573

1c Kagan HB. New J. Chem. 1990, 14: 453

1d Molander GA. Chem. Rev. 1992, 92: 29

1e Molander GA. Org. React. 1994, 46: 211

1f Molander GA. Harris CR. Chem. Rev. 1996, 96: 307

2a Yanada R. Negoro N. Yanada K. Fujita T. Tetrahedron Lett. 1997, 38: 3271

2b Lautens M. Delanghe PH. J. Org. Chem. 1995, 60: 2474

2c Taniguchi Y. Fujii N. Takaki K. Fujiwara Y. J. Orgmet. Chem. 1995, 491: 173

2d Yamazaki T. Lin JT. Takeda M. Kitazume T. Tetrahedron: Asymmetry 1990, 1: 351

2e Hou Z. Takamine K. Aoki O. Shiraishi H. Fujiwara Y. Taniguchi H. J. Org. Chem. 1988, 53: 6077

2f Yanada R. Negoro N. Bessho K. Yanada K. Synlett 1995, 1261

3 Hou Z. Taniguchi H. Fujiwara Y. Chem. Lett. 1987, 305

4a Clive DLJ. Daigneault S. J. Org. Chem. 1991, 56: 3801

4b Wang L. Zhang Y. Tetrahedron 1998, 54: 11129

4c Wang L. Zhang Y. Tetrahedron Lett. 1998, 39: 5257

4d Wang L. Zhang Y. Tetrahedron 1999, 55: 10695

4e Wang L. Zhou L. Zhang Y. Synlett 1999, 1065

4f Wang L. Li P. Zhou L. Tetrahedron Lett. 2002, 43: 8143

4g Yu C. Liu B. Hu L. J. Org. Chem. 2001, 66: 919

5a Yanada R. Negoro N. Yanada K. Fujita T. Tetrahedron Lett. 1996, 37: 9313

5b Yanada R. Ibuka T. J. Synth. Org. Chem. Jpn. 2000, 58: 597

5c Xu XL. Lu P. Zhang YM. Synth. Commun. 2000, 30: 1917

6a Corey EJ. Fuchs PL. Tetrahedron Lett. 1972, 3769

6b Ramirez F. Desai NB. McKelvie N. J. Am. Chem. Soc. 1962, 84: 1745

7a Roush WR. Koyama K. Curtin ML. Moriarty KJ. J. Am. Chem. Soc. 1996, 118: 7502

7b Roush WR. Reilly ML. Koyama K. Brown BB. J. Org. Chem. 1997, 62: 8708

8a Shen W. Wang L. J. Org. Chem. 1999, 64: 8873

8b Shen W. Wang L. Tetrahedron Lett. 1998, 39: 7625

9 Ratovelomanana V. Hammoud A. Linstrumelle G. Tetrahedron Lett. 1987, 1649

10a Minato A. Suzuki K. Tamao K. J. Am. Chem. Soc. 1987, 109: 1257

10b Minato A. J. Org. Chem. 1991, 56: 4052

11a Uenishi J. Kawahama R. Yonemitsu O. Tsuji J. J. Org. Chem. 1998, 63: 8965

11b Tietze LF. Nöble T. Spescha M. J. Am. Chem. Soc. 1998, 120: 8971

11c Uenishi J. Kawahama R. Yonemitsu O. Wada A. Ito M. Angew. Chem., Int. Ed. 1998, 37: 320

12 McAlonan H. Montgomery D. Stevenson P. Tetrahedron Lett. 1996, 37: 7151

13 Ranu BC. Samanta S. Guchhait SK. J. Org. Chem. 2001, 66: 4102

14 Kunishima M. Hioki K. Ohara T. Tani S. J. Chem. Soc., Chem. Commun. 1992, 219

Generation of alkylidenecarbenes from 1,1-dibromo-1-alkenes by the reaction with samarium diiodide in hexamethylphosphoric triamide-benzene has been reported and the rearranged alkynes was generated. See ref. 14 for details. Also generation of alkylidenecarbenes from 1,1-dibromo-1-alkenes by the the reaction with organolithiums or organozincates has been reported. See:

15a Köbrich G. Angew. Chem., Int. Ed. Engl. 1967, 6: 41

15b Harada T. Hara D. Hattori K. Oku A. Tetrahedron Lett. 1988, 29: 3821

Only activated alkenes, such as α,β-unsaturated carboxylic acid derivatives, and 1,1-dicyanoalkenes, can be reduced to the corresponding alkanes via 1,4-reduction hydrogenation with samarium diiodide. See:

16a Yacovan A. Hoz S. Bilkis I. J. Am. Chem. Soc. 1996, 118: 261

16b Yanada R. Bessho K. Yanada K. Synlett 1995, 443