title: Iridium-Catalyzed C-C Coupling of a Simple Propargyl Ether with Primary Alcohols: Enantioselective Homoaldol Addition via Redox-Triggered (Z)-Siloxyallylation.
abstract: A chiral iridium complex formed in situ from [Ir(cod)Cl]2 and (R)-H8-BINAP is found to catalyze the direct enantioselective C-C coupling of a simple propargyl ether, TIPSOCH2C≡CH, with primary alcohols to form γ-hydroxy (Z)-enol silanes with uniformly high enantioselectivity and complete alkene (Z)-stereoselectivity. As corroborated by deuterium labeling studies, these studies represent the first examples of 1,2-hydride shift-enabled π-allyl formation in the context of iridium catalysis.
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Tao
authors.initials: T
authors.lastname: Liang
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Wandi
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D010084:Oxidation-Reduction; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000447:Aldehydes; D012821:Silanes; D007495:Iridium; C116609:3-hydroxybutanal