Mechanistic insights into radical formation and functionalization in copper/N-fluorobenzenesulfonimide radical-relay reactions.

ABSTRACT: Copper-catalysed radical-relay reactions that employ N-fluorobenzenesulfonimide (NFSI) as the oxidant have emerged as highly effective methods for C(sp³)-H functionalization. Herein, computational studies are paired with experimental data to investigate a series of key mechanistic features of these reactions, with a focus on issues related to site-selectivity, enantioselectivity, and C-H substrate scope. (1) The full reaction energetics of enantioselective benzylic C-H cyanation are probed, and an adduct between Cu and the N-sulfonimidyl radical (˙NSI) is implicated as the species that promotes hydrogen-atom transfer (HAT) from the C-H substrate. (2) Benzylic versus 3° C-H site-selectivity is compared with different HAT reagents: Cu/˙NSI, ˙O^t

SUBMITTER: Mandal M 

PROVIDER: S-EPMC10806759 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature