Selective -Oxyamination and Hydroxylation of Aliphatic Amides

Compared to the -functionalization of aldehydes, ketones, even esters, the direct -modification of amides is still a challenge because of the low acidity of -CH groups. The -functionalization of N-H (primary and secondary) amides, containing both an unactived -C-H bond and a competitively active N-H bond, remains elusive. Shown herein is the general and efficient oxidative -oxyamination and hydroxylation of aliphatic amides including secondary N-H amides. This transition-metal-free chemistry with high chemoselectivity provides an efficient approach to -hydroxy amides. This oxidative protocol significantly enables the selective functionalization of inert -C-H bonds with the complete preservation of active N-H bond.National Basic Research Program of China (973 Program) [2015CB856600]; National Natural Science Foundation of China [21325206, 21632001]; National Young Top-notch Talent Support Program; Peking University Health Science Center [BMU20160541]SCI(E)ARTICLE4012307-123115