Corey–Fuchs反应 

Corey–Fuchs反应,又称Ramirez–Corey–Fuchs反应

四溴化碳三苯基膦反应,发生一碳同系化生成二烯烃,然后再用正丁基锂处理而得到末端炔烃[1][2][3]


Corey-Fuchs反应

反应由美国化学家 E. J. Corey 和 Philip L. Fuchs 的名字命名。与早期 Desai 等[4] 制取二溴烯烃的方法相比,粉的加入促进了叶立德中间体的生成,从而减少了三苯基膦的用量,分离更易,产率更高。对于敏感的底物,需用三乙胺代替锌才能取得较好的效果。[5]

选用适宜的碱,可使反应也可停在1-溴代炔一步。溴代炔和末端炔烃是有机合成中很有用的官能团。[6]

近来工业界发展了三氯乙酸的等价合成方法,解决了大量合成中副产物三苯基氧膦的难处理问题,使反应用于大规模的制备。[7]

  1. ^ Corey, E. J.; Fuchs, P. L. A synthetic method for formyl → ethynyl conversion (RCHO → RCCH or RCCR′). Tetrahedron Lett. 1972, 13 (36): 3769–3772. doi:10.1016/S0040-4039(01)94157-7. 
  2. ^ Mori, M.; Tonogaki, K.; Kinoshita, A. "Synthesis of 1,3-Dienes from Alkynes and Ethylene: Acetic Acid 2-Methylene-3-phenethylbut-3-enyl Ester 页面存档备份,存于互联网档案馆". Organic Syntheses, Vol. 81, p.1 (2005).
  3. ^ Marshall, J. A.; Yanik, M. M.; Adams, N. D.; Ellis, K. C.; Chobanian, H. R. "Generation of Nonracemic 2-(t-Butyldimethylsilyloxy)-3-butynyllithium from (S)-Ethyl Lactate 页面存档备份,存于互联网档案馆". Organic Syntheses, Vol. 81, p.157 (2005).
  4. ^ N. B. Desai, N. McKelvie. A New Synthesis of 1,1-Dibromoölefins via Phosphine-Dibromomethylenes. the Reaction of Triphenylphosphine with Carbon Tetrabromide. J. Am. Chem. Soc. 1962, 84 (9): 1745–1747. doi:10.1021/ja00868a057. 
  5. ^ D. Grandjean, P. Pale and J. Chuche. An improved procedure for aldehyde-to-alkyne homologation via 1,1-dibromoalkenes; synthesis of 1-bromoalkynes. Tetrahedron Letters. 1994, 35 (21): 3529–3530. doi:10.1016/S0040-4039(00)73227-8. 
  6. ^ Craig M. Williams and Lewis N. Mander. Bridgehead Arylation: A Direct Route to Advanced Intermediates for the Synthesis of C-20 Diterpene Alkaloids. Org. Lett. 2003, 5 (19): 3499–3502. doi:10.1021/ol0353060. 
  7. ^ Zhe Wang, Silvio Campagna, Kaihong Yang, Guoyou Xu, Michael E. Pierce, Joseph. M. Fortunak, and Pat. N. Confalone. A Practical Preparation of Terminal Alkynes from Aldehydes. J. Org. Chem. 2000, 65 (6): 1889–1891. doi:10.1021/jo9916582. 



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