Chiral Primary Amine/Ketone Cooperative Catalysis for Asymmetric ?-Hydroxylation with Hydrogen Peroxide

Carbonyls and amines are yin yang in organocatalysis as they mutually activate transform each other. These intrinsically reacting partners tend to condense with other, thus depleting their individual activity when used together cocatalysts. Though widely established many prominent catalytic strategies, aminocatalysis carbonyl catalysis do not coexist well, and, such, a cooperative amine/carbonyl dual remains essentially unknown. Here we report primary amine ketone approach for the asymmetric ?-hydroxylation of ?-ketocarbonyls H2O2. Besides participating typical enamine cycle, chiral catalyst was found work cooperatively H2O2 via an oxaziridine intermediate derived from in-situ-generated ketimine. Ultimately, this enamine–oxaziridine coupling facilitated highly controlled several excellent yield enantioselectivity. Notably, late-stage hydroxylation peptidyl amide or esters can also be achieved high stereoselectivity. In addition its operational simplicity mild conditions, amine/ketone provides new strategy activation expands domain include challenging transformation.