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 th...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 ofγ-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.Apossiblereaction pathwaywas provided tounderstandα-selectivity overy-selectivity.展开更多
基金This work is supported by the National Natural Science Foundation of China(No.21890723)Sichuan University(2020SCUNL204).
文摘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 ofγ-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.Apossiblereaction pathwaywas provided tounderstandα-selectivity overy-selectivity.