p-Methoxybenzyl-Radical-Promoted Chemoselective Protection of sec-Alkylamides

Abstract

The hitherto difficult site-selective p-methoxybenzylation of secondary amides using p-methoxybenzylated alkylsilyl peroxides as a novel p-methoxybenzylation agent under copper catalysis is reported. The reaction proceeds under mild reaction conditions in a highly chemoselective manner. This approach was successfully applied to the site-selective p-methoxybenzylation of peptides.

Site-selective editing of peptides via backbone modification

“…Maruoka and colleagues reported a radical-promoted p -methoxybenzylation of secondary amides using alkylsilyl peroxides as benzylation reagents (Scheme 11). 17 The reaction proceeds in a highly chemically selective manner under relatively mild conditions, allowing for site-selective benzylation of short peptides.…”