title: Diastereo- and enantioselective anti-alkoxyallylation employing allylic gem-dicarboxylates as allyl donors via iridium-catalyzed transfer hydrogenation.
abstract: Enantioselective transfer hydrogenation of gem-dibenzoate 1e in the presence of aromatic, alpha,beta-unsaturated, or aliphatic aldehydes 2a-i mediated by isopropyl alcohol and employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, 4-cyano-3-nitrobenzoic acid, and (R)-SEGPHOS delivers products of alkoxyallylation 3a-i, 4a, 4e, 4f, and 4i in good isolated yields (62-82%) with good to excellent diastereoselectivities (7:1 to 18:1 dr) and exceptional enantioselectivities (90-99% ee). This protocol provides an alternative to the use of premetalated nucleophiles in carbonyl alkoxyallylation.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
authors.forename: Soo Bong
authors.initials: SB
authors.lastname: Han
authors.forename: Hoon
authors.initials: H
authors.lastname: Han
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000085:Acetates / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D019817:Benzoic Acid / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D006865:Hydrogenation; D007495:Iridium / Q000737:chemistry*; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000085:Acetates; D000447:Aldehydes; D000475:Alkenes; D002264:Carboxylic Acids; D010720:Phosphines; D007495:Iridium; D019817:Benzoic Acid; C044646:phosphine