论文部分内容阅读
Density functional theory calculations have been performed to investigate the dipeptide phosphine-catalyzed hydroamination of enones with pyridazinones.The computations reveal that a number of the N-H…O hydrogen-bonding interactions with the pyridazinone moiety and the C-H…O hydrogen-bonding interactions with the enone moiety are present in the enantioselectivity-determining Michael addition transition states.The experimentally-observed catalyst-controlled enantiodivergence is mainly attributed to the significant impact of the substituent of the amide moiety of the dipeptide phosphine on the relative strength of the N-H…O hydrogen-bonding interactions,which was found to affect the Si face attack transition state,enabling the enantioselectivity switch upon change of chiral dipeptide phosphine catalyst.