奥弗曼重排反应
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奥弗曼重排反应(英語:Overman rearrangement)是三氯乙酰亚胺烯丙酯在热或金属(如Hg(II)、Pd(II))催化下发生重排,得到三氯乙酰氨基烯烃的反應。[1][2][3][4]
![奥弗曼重排反應](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/2/20/Overman_Rearrangement_scheme.svg/500px-Overman_Rearrangement_scheme.svg.png)
1974年由美国化学家拉里·奥弗曼首先报道。
该反应是对克莱森重排反应和科普重排反应的补充和机理的证明。反应产物烯丙胺经转化可以得到许多含氮的天然产物和生物分子。[5]
反应机理
热重排机理:与克莱森重排反應机理类似,是同面协同的[3,3]-σ迁移反应。
![热奥弗曼重排反應](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/9/9c/Thermo-Overman_rearrangement_mechanism.svg/600px-Thermo-Overman_rearrangement_mechanism.svg.png)
金属汞催化机理:氮汞键对双键插入和氧汞消除的历程,只是一个形式上的[3,3]-σ键重排。
![金属汞催化的奥弗曼重排反應](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/d/d8/Mercury-catalysed_Overman_rearrangement_mechanism.svg/600px-Mercury-catalysed_Overman_rearrangement_mechanism.svg.png)
参见
参考资料
- ^ Larry E. Overman. A general method for the synthesis of amines by the rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions. J. Am. Chem. Soc. 1976, 98: 2901–2910. doi:10.1021/ja00426a038.
- ^ Overman, L. E. Allylic and propargylic imidic esters in organic synthesis. Accounts of Chemical Research. 1980, 13: 218–224. doi:10.1021/ar50151a005.
- ^ Organic Syntheses, Coll. Vol. 6, p.507; Vol. 58, p.4 (Article (页面存档备份,存于互联网档案馆))
- ^ Overman, L. E. Thermal and mercuric ion catalyzed [3,3]-sigmatropic rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions. Journal of the American Chemical Society. 1974, 96: 597–599. doi:10.1021/ja00809a054.
- ^ Chen, Y. K.; Lurain, A. E.; Walsh, P. J. A General, Highly Enantioselective Method for the Synthesis of D and L α-Amino Acids and Allylic Amines. Journal of the American Chemical Society. 2002, 124: 12225–12231. doi:10.1021/ja027271p.
- ^ Anderson, C. E.; Overman, L. E. J. Am. Chem. Soc. 2003, 125, 12412–12413. (doi:10.1021/ja037086r)
- ^ Asymmetric Overman Rearrangement Organic Syntheses, Vol. 82, p.134 (2005). (Article (页面存档备份,存于互联网档案馆))
延伸阅读
- Isobe, M. et al. Tetrahedron Lett. 1990, 31, 3327.
- Allmendinger, T. et al. Tetrahedron Letters 1990, 31, 7301.
- Nishikawa, T.; Asai, M.; Ohyabu, N.; Isobe, M.; J. Org. Chem. 1998, 63(1), 188-192. PMID 11674062 )