title: Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides.
abstract: The enantioselective desymmetrization of cyclic meso-anhydrides with benzyl trifluoroborates under nickel-photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto-acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni-C bond homolysis of a NiIIadduct is proposed. This feature allows access to a trans keto-acid as the major product in high enantioselectivity from a cis meso anhydride.
authors.affiliation: Department of Chemistry, Princeton University, 120 Washington Road, Princeton, NJ, 08544, USA.|Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.
authors.forename: Erin E
authors.initials: EE
authors.lastname: Stache
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.|Department of Chemistry, Columbia University, New York, NY, 10027, USA.
authors.forename: Tomislav
authors.identifier: 0000-0001-6287-8669
authors.initials: T
authors.lastname: Rovis
authors.affiliation: Department of Chemistry, Princeton University, 120 Washington Road, Princeton, NJ, 08544, USA.
authors.forename: Abigail G
authors.initials: AG
authors.lastname: Doyle
mesh_terms: D000812:Anhydrides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D007651:Keto Acids / Q000138:chemical synthesis* / Q000737:chemistry; D008027:Light; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D013237:Stereoisomerism
chemical_list: D000812:Anhydrides; D007651:Keto Acids; D009532:Nickel
keywords: asymmetric synthesis; cross-coupling; desymmetrization; nickel; photoredox catalysis