Iridium-Catalyzed Migratory Terminal C(sp³)-H Amidation of Heteroatom-Substituted Internal Alkenes via Olefin Chain Walking

Abstract

Hydroamination facilitated by metal hydride catalysis is an appealing synthetic approach to access valuable nitrogen-containing compounds from readily available unsaturated hydrocarbons. While high regioselectivity can be achieved usually for substrates bearing polar chelation groups, the reaction involving simple alkenes frequently provides nonselective outcomes. Herein, we report an iridium-catalyzed highly regioselective terminal C-(sp(3))-H amidation of internal alkenes utilizing dioxazolones as an amino source via olefin chain walking. Most notably, this mechanistic motif of double bond migration to the terminal position operates not only with dialkyl-substituted simple alkenes including styrenes but also with heteroatom-substituted olefins such as enol ethers, vinyl silanes, and vinyl borons, thus representing the first example of the terminal methyl amidation of the latter type of alkenes through a nondissociative chain walking process.