Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the gamma-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline (L4) as the ligand and dioxazolones as the reagent, the amidation occurs at the gamma-C(sp(3))-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).

Automated summary

A NiH-catalyzed thioether-directed cyclometalation strategy allows for remote methylene C-H bond amidation of unactivated alkenes. This strategy shows high yields and remarkable regioselectivity in the preparation of amide products.