Asymmetric Catalytic <scp>α‐Selective</scp> Allylation of Ketones with Allyltrifluoroborates Using <scp>Dual‐Functional</scp> Chiral <scp>In<sup>III</sup></scp>/<i>N</i>,<i>N</i>′‐Dioxide Complex
Xiaoxue Tang, Zhishan Su, Qianchi Lin, Lili Lin, Shunxi Dong, Xiaoming Feng
Abstract
Comprehensive Summary Asymmetric 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 In III / 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 In III / 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.