Computational Exploration of Dirhodium Complex-Catalyzed Selective Intermolecular Amination of Tertiary vs. Benzylic C-H Bonds.

ABSTRACT: The mechanism and origins of site-selectivity of Rh₂(S-tfpttl)₄-catalyzed C(sp³)-H bond aminations were studied using density functional theory (DFT) calculations. The synergistic combination of the dirhodium complex Rh₂(S-tfpttl)₄ with tert-butylphenol sulfamate TBPhsNH₂ composes a pocket that can access both tertiary and benzylic C-H bonds. The nonactivated tertiary C-H bond was selectively aminated in the presence of an electronically activated benzylic C-H bond. Both singlet and triplet energy surfaces were investigated in this study. The computational results suggest that the triplet stepwise pathway is more favorable than the singlet concerted pathway. In the hydrogen atom abstraction by Rh-

SUBMITTER: Su XX 

PROVIDER: S-EPMC9959850 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature