Catalytic asymmetric construction of 1,5-remote Si- and C-stereocenters via desymmetrizing ene reaction of bis(methallyl)silanes

Abstract

The catalytic enantioselective synthesis of chiral silanes has long been a challenging pursuit. Achieving simultaneous construction of remote Si- and C-stereogenic centers in an acyclic molecule via desymmetrization is particularly difficult. Herein, we realized an example of a chiral nickel(II) complex-catalyzed desymmetrizing carbonyl–ene reaction of bis(methallyl)silanes with α-keto aldehyde monohydrates, enabling the highly chemo-, diastereo- and enantioselective synthesis of chiral δ-hydroxy silanes featuring 1,5-remote Si- and C-stereocenters. This protocol demonstrated good functional group tolerance and a broad substrate scope. A bioactivity study revealed its potential applications in the synthesis of bioactive molecules.