title: Iridium-catalyzed allylation of chiral β-stereogenic alcohols: bypassing discrete formation of epimerizable aldehydes.
abstract: The cyclometalated π-allyliridium 3,4-dinitro-C,O-benzoate complex modified by (R)- or (S)-Cl,MeO-BIPHEP promotes the transfer hydrogenative coupling of allyl acetate to β-stereogenic alcohols with good to excellent levels of catalyst-directed diastereoselectivity to furnish homoallylic alcohols. Remote electronic effects of the C,O-benzoate of the catalyst play a critical role in suppressing epimerization of the transient α-stereogenic aldehyde.
authors.affiliation: University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, United States.
authors.forename: Daniel C
authors.initials: DC
authors.lastname: Schmitt
authors.forename: Anne-Marie R
authors.initials: AM
authors.lastname: Dechert-Schmitt
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000447:Aldehydes; D007495:Iridium