CuH-catalyzed stereoselective desymmetrization of prochiral cyclopentane-1,3-diones <i>via</i> alkoxyallylation

We report a CuH-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted cyclopentane-1,3-diones through reductive alkoxyallylation. This strategy exploits the carbonyl group, an underexplored reactivity mode for the desymmetrization of cyclopentane-1,3-diones, constructing complex chiral carbocycles from simple symmetric diketones. This efficient, atom-economic transformation delivers functionalized cyclopentanones, bearing three consecutive stereocenters, including two quaternary carbons in a single operation. The protocol exhibits broad substrate scope, high diastereoselectivity, and moderate to good enantioselectivity.