Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

作者：Goh Shermin S; Guduguntla Sureshbabu; Kikuchi Takashi; Lutz Martin; Otten Edwin; Fujita Makoto; Feringa Ben L^*

来源：Journal of the American Chemical Society, 2018, 140(23): 7052-7055.

DOI：10.1021/jacs.8b02992

The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated by the concise stereocontrolled preparation of cyclic amino alcohols, which are privileged chiral structures in natural products and pharmaceuticals and widely used in synthesis and catalysis.

• 出版日期2018-6-13