title: Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds.
abstract: We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.
authors: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors: Hatice G
authors: HG
authors: Yayla
authors: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors: Huaiju
authors: H
authors: Wang
authors: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors: Kyle T
authors: KT
authors: Tarantino
authors: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors: Hudson S
authors: HS
authors: Orbe
authors: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors: Robert R
authors: RR
authors: Knowles
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D004579:Electron Transport; D006859:Hydrogen / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*
chemical_list: D000438:Alcohols; D006859:Hydrogen; D010100:Oxygen