通过α-卤代-β,β-二氟苯乙烯的铃木偶联反应制备2,2-二芳基-1,1-二氟-1-烯烃和1,1-二氟-2-芳基-1,3-二烯的新有效方法。

New efficient approach to 2,2-diaryl-1,1-difluoro-1-alkenes and 1,1-difluoro-2-aryl-1,3-dienes via Suzuki coupling of alpha-halo-beta,beta-difluorostyrenes.

作者信息

Raghavanpillai Anilkumar, Burton Donald J

机构信息

Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA.

出版信息

J Org Chem. 2006 Jan 6;71(1):194-201. doi: 10.1021/jo051842p.

DOI:10.1021/jo051842p

PMID:16388635

Abstract

[reaction: see text] Alpha-halo-beta,beta-difluorostyrenes [ArCX = CF2; X = Br, I; Ar = aryl, heteroaryl; synthesized by the Pd(0)-catalyzed coupling reaction of the corresponding alpha-halo-beta,beta-difluoroethenylzinc reagents (CF2=CXZnCl, X = Br, I) with aryl iodides] were functionalized at the halogen site with arylboronic acids under Pd(0)-catalyzed Suzuki-Miyaura coupling reaction conditions to obtain 2,2-diaryl-1,1-difluoro-1-alkenes (ArAr'C=CF2, Ar' = aryl, heteroaryl) in 51-91% isolated yield. The corresponding reaction with alkenylboronic acids produced 1,1-difluoro-2-aryl-1,3-dienes in 53-80% isolated yield. Alternatively, 2,2-disubstituted-1,1-difluoro-1-alkenes were synthesized in moderate yield by a zinc-insertion reaction at the halogen site of the alpha-halo-beta,beta-difluorostyrenes, followed by Pd(0)-catalyzed cross-coupling of the zinc reagent with aryl or alkenyl iodides.

摘要

[反应：见正文] α-卤代-β,β-二氟苯乙烯[ArCX = CF₂；X = Br、I；Ar = 芳基、杂芳基；通过相应的α-卤代-β,β-二氟乙烯基锌试剂（CF₂=CXZnCl，X = Br、I）与芳基碘化物的钯(0)催化偶联反应合成]在钯(0)催化的铃木-宫浦偶联反应条件下，在卤素位点用芳基硼酸进行官能团化反应，以51%至91%的分离产率得到2,2-二芳基-1,1-二氟-1-烯烃（ArAr'C=CF₂，Ar' = 芳基、杂芳基）。与烯基硼酸的相应反应以53%至80%的分离产率生成1,1-二氟-2-芳基-1,3-二烯。或者，通过在α-卤代-β,β-二氟苯乙烯的卤素位点进行锌插入反应，然后钯(0)催化锌试剂与芳基或烯基碘化物的交叉偶联反应，以中等产率合成2,2-二取代-1,1-二氟-1-烯烃。