Remote Nucleophilic Substitution at a C(sp 3 )-H Bond of α-Bromocarboxamides via 1,4-Hydrogen Atom Transfer To Access N -Acyl- N , O -acetal Compounds.

Herein, we report a remote nucleophilic substitution reaction via 1,4-hydrogen atom transfer (1,4-HAT) to synthesize N -acyl- N , O -acetal moieties. α-Bromocarboxamide undergoes rS N at a C(sp 3 )-H bond in the presence of an alcohol/phenol and a copper catalyst. Mechanistic studies using deuterated α-bromocarboxamide confirmed that the 1,4-HAT process is the rate-determining step. Topologically complex N -acyl- N , O -acetal molecules can be accessed using our rS N reaction with various α-bromocarboxamides via chemoselective reactions.