A DFT Study on CuH-Catalyzed Reductive Relay Hydroamination for Synthesis of Remote-Chiral Amine

作者：Gao, Yun; Wang, Ping; Zhao, Yang; Liu, Qingyun^*; Liu, Wei^*; Wang, Yong^*

来源：ChemistrySelect, 2018, 3(7): 2157-2161.

DOI：10.1002/slct.201800367

• Density functional theory
• Enantioselectivity
• Hydroamination
• Mechanism

The reaction mechanism of copper-hydride-catalyzed reductive relay hydroamination for remote-chiral amine was studied. Using density functional theory, we carefully investigated the mechanistic of the generation of R- and S-amines with stereocenters. A series of steps, such as Markovnikov hydrocupration, beta-alkoxide elimination of alkylcopper, insertion of terminal alkene with copper-hydride catalyst, the electrophile attack, and the formation of C-N bonds have been discussed in the catalytic cycle. The most favorable pathway is obtained by the Re-attack of the catalyst with the allylic ester. In addition, noncovalent interaction (NCI) analyses show stronger noncovalent interactions in transition state Re-TS1, frontier molecular orbital (FMO) reveal a larger lowest unoccupied molecular orbital and the highest occupied molecular orbital (LUMO-HOMO) gap in transition state Si-TS1, indicating the preference for the S-configuration chiral amines, which is in good agreement with the experimental observations.

• 出版日期2018-2-21
• 单位山东科技大学; 苏州大学