Controllable carbonyl-assisted C(sp(3))-C(sp(3)) bond reduction and reorganization

C-C bond reduction and reorganization are fundamentally important in organic synthesis. However, there are no practical methods for tandem C-C reduction and reorganization. Here we report a versatile approach for selective reduction of the unstrained C(sp(3))-C(sp(3)) bond of ketones, including hydrogenolytic [2 + 2 + 2]-cycloreversion of 2,4-diaroylcyclohexanols, without requiring protecting groups or hydrogen gas. Mechanistic data demonstrate that the C-C cleavage occurs via a bimetallic pathway, and nucleophile trapping of the resulting enone is crucial for C-C reduction relay. Moreover, a practical strategy for intramolecular C-C cascade reorganization is established via iterative retro-Michael/intramolecular Michael addition sequence, thus enabling cyclizative degradation of poly(vinylketone) to trisubstituted cyclohexanes. These results could open new prospects for unstrained C(sp(3))-C(sp(3)) bond disconnection and reconstruction.