醛的亲核溴代和碘代二氟甲基化反应

Nucleophilic bromo- and iododifluoromethylation of aldehydes.

作者信息

Kosobokov Mikhail D, Levin Vitalij V, Struchkova Marina I, Dilman Alexander D

机构信息

N. D. Zelinsky Institute of Organic Chemistry, 119991 Moscow, Leninsky prosp. 47, Russian Federation.

出版信息

Org Lett. 2014 Jul 18;16(14):3784-7. doi: 10.1021/ol501674n. Epub 2014 Jun 26.

DOI:10.1021/ol501674n

PMID:24968144

Abstract

A method for bromo- and iododifluoromethylation of aldehydes using bromo- and iodo-substituted difluoromethyl silicon reagents (Me(3)SiCF(2)X) is described. The reaction is performed in the presence of a combination of tetrabutylammonium and lithium salts Bu(4)NX/LiX (X = Br or I) in propionitrile. It is believed that, in this process, a short-lived halodifluoromethyl carbanion serves as nucleophile, which is reversibly generated from difluorocarbene and a halide anion.

摘要

描述了一种使用溴代和碘代二氟甲基硅试剂（Me(3)SiCF(2)X）对醛进行溴代和碘代二氟甲基化的方法。该反应在四丁基铵盐和锂盐Bu(4)NX/LiX（X = Br或I）的组合存在下于丙腈中进行。据信，在此过程中，一种短寿命的卤代二氟甲基碳负离子作为亲核试剂，它由二氟卡宾和卤离子可逆生成。