奧弗曼重排反應
![本頁使用了標題或全文手工轉換](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/c/cd/Zh_conversion_icon_m.svg/35px-Zh_conversion_icon_m.svg.png)
奧弗曼重排反應(英語:Overman rearrangement)是三氯乙酰亞胺烯丙酯在熱或金屬(如Hg(II)、Pd(II))催化下發生重排,得到三氯乙酰氨基烯烴的反應。[1][2][3][4]
![奧弗曼重排反應](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/2/20/Overman_Rearrangement_scheme.svg/500px-Overman_Rearrangement_scheme.svg.png)
1974年由美國化學家拉里·奧弗曼首先報道。
該反應是對克萊森重排反應和科普重排反應的補充和機理的證明。反應產物烯丙胺經轉化可以得到許多含氮的天然產物和生物分子。[5]
反應機理
熱重排機理:與克萊森重排反應機理類似,是同面協同的[3,3]-σ遷移反應。
![熱奧弗曼重排反應](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)
金屬汞催化機理:氮汞鍵對雙鍵插入和氧汞消除的歷程,只是一個形式上的[3,3]-σ鍵重排。
![金屬汞催化的奧弗曼重排反應](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)
參見
參考資料
- ^ 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 (頁面存檔備份,存於互聯網檔案館))
- ^ 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 (頁面存檔備份,存於互聯網檔案館))
延伸閱讀
- 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 )