title: Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.
abstract: Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition.
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Victoria J
authors.initials: VJ
authors.lastname: Garza
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: D000085:Acetates / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D005557:Formaldehyde / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry; D008745:Methylation; D010084:Oxidation-Reduction; D020005:Propanols / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000498:Allyl Compounds; D020005:Propanols; D005557:Formaldehyde; C006463:allyl alcohol; D007495:Iridium