Diverse secondary C(sp3)-H bond functionalization via site-selective trifluoroacetoxylation of aliphatic aminesElectronic supplementary information (ESI) available: Experimental details and compound characterization. See DOI: 10.1039/c8sc01788c

We describe a coinage-metal-catalyzed site-selective oxidation of secondary C(sp 3 )-H bonds for aliphatic amine substrates. Broad amine scope, good functional compatibility and late-stage diversification are demonstrated with this method. The steric demand of the β-substituents controlled diastereoselectivities under this catalytic system. The site selectivity favors secondary C(sp 3 )-H bonds over tertiary ones underscoring the unique synthetic potential of this method. A coinage-metal-catalyzed site-selective trifluoroacetoxylation of remote secondary C(sp 3 )-H bonds for aliphatic amine substrates was developed.