Origins of catalyst-controlled enantiodivergent hydroamination of enones with pyridazinones:A computational study  

作　　者：Xiangwei Ren Hongli Wu Mei Zhang Wentao Zhao Genping Huang 

机构地区：[1]Department of Chemistry,School of Science and Tianjin Key Laboratory of Molecular Optoelectronic Sciences,Tianjin University,Tianjin 300072,China

出　　处：《Chinese Chemical Letters》2021年第9期2769-2772,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.22073066,21503143 and 21975179);the Natural Science Foundation of Tianjin(No.16JCQNJC05600)。

摘　　要：Density functional theory calculations have been performed to investigate the dipeptide phosphinecatalyzed 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 hydrogenbonding 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.

关 键 词：Dipeptide phosphine catalyst HYDROAMINATION Mechanism Selectivity DFT calculations 

分 类 号：O621.251[理学—有机化学]