Iridium-catalyzed enantioselective alkynylation and kinetic resolution of alkyl allylic alcohols

Abstract

Herein, we report an efficient kinetic resolution of alkyl allylic alcohols enabled by an iridium-catalyzed enantioselective alkynylation of alkyl allylic alcohols with potassium alkynyltrifluoroborates. A wide range of chiral 1,4-enynes bearing various functional groups and unreacted enantioenriched allylic alcohols were obtained with excellent enantioselectivities and high kinetic resolution performance (s-factor up to 922). Additionally, this method is particularly effective for preparing some useful optically pure alkyl allylic alcohols, such as the key components towards the synthesis of prostaglandins and naturally occurring matsutakeols, which are difficult to access via other asymmetric reactions. Mechanistic studies revealed that the efficient kinetic resolution might be due to the significant distinction of the η²-coordination between the (R)- and (S)-allylic alcohols with the iridium/(phosphoramidite, olefin) complex.