Asymmetric Catalytic α‐Selective Allylation of Ketones with Allyltrifluoroborates Using Dual‐Functional Chiral InIII/N,N′‐Dioxide Complex

Abstract

Comprehensive SummaryAsymmetric catalytic allylation of halo‐substituted ketones and ketoesters was accomplished to yield a number of homoallylic tertiary alcohols in excellent reactivity and enantioselectivity. In the presence of chiral InIII/N,N′‐dioxide catalyst, unusual α‐selective allylation of γ‐substituted potassium allyltrifluoroborates to ketones was demonstrated. The control experiments and DFT calculation reveal that chiral InIII/N,N′‐dioxide catalyst plays dual‐tasking roles: the formation of allylindium species via transmetalation and Lewis acid activation. A possible reaction pathway was provided to understand α‐selectivity over γ‐selectivity.