title: P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters.
abstract: A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.
authors.affiliation: Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
authors.forename: Sunewang Rixin
authors.initials: SR
authors.lastname: Wang
authors.affiliation: Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
authors.forename: Alexander T
authors.initials: AT
authors.lastname: Radosevich
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry; D002384:Catalysis; D004952:Esters; D006842:Hydrocarbons, Brominated / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D000498:Allyl Compounds; D004952:Esters; D006842:Hydrocarbons, Brominated; D009943:Organophosphorus Compounds; C050431:allyl bromide