title: Enantio-, diastereo-, and regioselective iridium-catalyzed asymmetric allylic alkylation of acyclic β-ketoesters.
abstract: The first regio-, diastereo-, and enantioselective allylic alkylation of acyclic β-ketoesters to form vicinal tertiary and all-carbon quaternary stereocenters is reported. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands. Broad functional group tolerance is observed at the keto-, ester-, and α-positions of the nucleophile. Various transformations demonstrating the utility of this method for rapidly accessing complex enantioenriched compounds are reported.
authors.affiliation: Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Wen-Bo
authors.initials: WB
authors.lastname: Liu
authors.forename: Corey M
authors.initials: CM
authors.lastname: Reeves
authors.forename: Brian M
authors.initials: BM
authors.lastname: Stoltz
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D000478:Alkylation; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000179:Acrylates; D000498:Allyl Compounds; D004952:Esters; D007659:Ketones; D009942:Organometallic Compounds; D007495:Iridium