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

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