DFT Mechanistic Account for the Site Selectivity of Electron-Rich C(sp3)-H Bond in the Manganese-Catalyzed Aminations

Zheyuan Liu; Yu Lu; Jiandong Guo; Wenping Hu; Yanfeng Dang; Zhi-Xiang Wang

doi:10.1021/acs.orglett.9b04215

DFT Mechanistic Account for the Site Selectivity of Electron-Rich C(sp³)-H Bond in the Manganese-Catalyzed Aminations

Org Lett. 2020 Jan 17;22(2):453-457. doi: 10.1021/acs.orglett.9b04215. Epub 2020 Jan 8.

Authors

Zheyuan Liu¹, Yu Lu², Jiandong Guo², Wenping Hu¹, Yanfeng Dang¹, Zhi-Xiang Wang²

Affiliations

¹ Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry , Tianjin University , Tianjin 300072 , China.
² School of Chemical Sciences , University of the Chinese Academy of Sciences , Beijing 100049 , China.

PMID: 31913046
DOI: 10.1021/acs.orglett.9b04215

Abstract

DFT study suggests that the C-H cleavage involved in the C(sp³)-H amination catalyzed by manganese perchlorophthalocyanine complex [Mn^III(ClPc)]⁺ proceeds via hydride transfer (HYT), instead of hydrogen atom transfer (HAT), thus elucidating why the reaction favors aminating the electron-rich C-H bond, rather than that with smaller bond dissociation energy preferred by HAT. Detailed analyses indicate the HYT actually occurs via concerted electron and hydrogen atom transfers and the redox-active ClPc ligand enables the HYT.

Publication types

Research Support, Non-U.S. Gov't