Photocatalytic deconstructive aliphatic carbon-carbon bond cleavage and functionalization of unactivated alcohols

Carbon-carbon (C-C) bonds are challenging to selectively cleave owing to their chemical inertness and omnipresence in organic mol-ecules; however, they can be targeted during the late-stage modifi-cation of natural products and active pharmaceutical ingredients. Herein, we report a selective deconstructive C(sp3)-C(sp3) bond cleavage and difunctionalization of unactivated alcohols mediated by a vanadium visible-light photocatalyst under ambient tempera-tures and pressures. Our base metal photocatalyst operates via ligand-to-metal charge transfer followed by an inner-sphere C-C bond cleavage to generate alkyl radicals that are trapped with SOMOphiles. We achieved 10 different bond formations on 44 ex-amples using a range of commercially sourced alcohols, including natural products and biomolecules. Our protocol can also be used for the regio-and diastereoselective cyclization to form an a-amino-lactone, and for the late-stage functionalization of bioactive oligo-peptides to access unnatural amino acid residues.