Concomitant functionalization of two different ketones by merging Brønsted acid catalysis and radical relay coupling

n the previous literature, incorporation of functional groups at the α-position of unactivated carbonylcompounds was mainly restricted to one kind of corresponding precursor. Herein, we report the concomitant functionalization of two distinct α-C–H bonds of carbonyls integrated with unactivated olefins andtert-butyl hydroperoxide selectively and efficiently in one pot by merging Brønsted acid catalysis andradical relay coupling, which delivers an array of structurally valuable unsymmetrical peroxy 1,9-diketonesin moderate to good yields under metal-free conditions.