P(NMe2)3‑Mediated Umpolung Alkylation and Nonylidic Olefination of α‑Keto Esters

P(NMe2)3‑Mediated Umpolung Alkylation and Nonylidic Olefination of α‑Keto Esters

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 th...

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Veröffentlicht in:Organic letters 2015-08, Vol.17 (15), p.3810-3813
Hauptverfasser: Wang, Sunewang Rixin, Radosevich, Alexander T
Format: Artikel
Sprache:eng
Schlagworte:
Alkenes - chemistry
Alkylation
Allyl Compounds - chemistry
Catalysis
Esters
Hydrocarbons, Brominated - chemical synthesis
Hydrocarbons, Brominated - chemistry
Magnetic Resonance Spectroscopy
Molecular Structure
Organophosphorus Compounds - chemistry
Oxidation-Reduction
Stereoisomerism
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Zusammenfassung: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.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.5b01784