Computational insights into Ir(iii)-catalyzed allylic C-H amination of terminal alkenes: mechanism, regioselectivity, and catalytic activity.

ABSTRACT: Computational studies on Ir(iii)-catalyzed intermolecular branch-selective allylic C-H amination of terminal olefins with methyl dioxazolone have been carried out to investigate the mechanism, including the origins of regioselectivity and catalytic activity difference. The result suggests that the reaction proceeds through generation of active species, alkene coordination, allylic C-H activation, decarboxylation, migratory insertion, and protodemetalation. The presence of AgNTf₂ could thermodynamically promote the formation of catalytically active species [Cp*Ir(OAc)]⁺. Both the weaker Ir-C(internal) bond and the closer interatomic distance of N⋯C(internal) in the key allyl-Ir(v)-nitrenoid intermediate make the migratory insertion into Ir-C(internal) bond easier than

SUBMITTER: Pan D 

PROVIDER: S-EPMC9033584 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature