title: Enantioselective Formation of All-Carbon Quaternary Centers via C-H Functionalization of Methanol: Iridium-Catalyzed Diene Hydrohydroxymethylation.
abstract: The first catalytic enantioselective C-C couplings of methanol (>30 × 106tons/year) are reported. Insertion of 2-substituted dienes into the methanol C-H bond occurs in a regioselective manner to form all-carbon quaternary centers with excellent levels of enantioselectivity using an iridium-PhanePhos catalyst. Mechanistic studies corroborate a Curtin-Hammett scenario in which methanol dehydrogenation triggers rapid, reversible diene hydrometalation en route to regioisomeric allyliridium-formaldehyde pairs, yet single constitutional isomers are formed.
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Khoa D
authors.initials: KD
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Daniel
authors.initials: D
authors.lastname: Herkommer
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: D000475:Alkenes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry*; D008745:Methylation; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D007495:Iridium; D002244:Carbon; D006859:Hydrogen; D000432:Methanol