title: Iridium-catalysed direct C-C coupling of methanol and allenes.
abstract: Methanol is an abundant (35 million metric tons per year), renewable chemical feedstock, yet its use as a one-carbon building block in fine chemical synthesis is highly underdeveloped. Using a homogeneous iridium catalyst developed in our laboratory, methanol engages in a direct C-C coupling with allenes to furnish higher alcohols that incorporate all-carbon quaternary centres, free of stoichiometric by-products. A catalytic mechanism that involves turnover-limiting methanol oxidation, a consequence of the high energetic demand of methanol dehydrogenation, is corroborated through a series of competition kinetics experiments. This process represents the first catalytic C-C coupling of methanol to provide discrete products of hydroxymethylation.
authors: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
authors: Joseph
authors: J
authors: Moran
authors: Angelika
authors: A
authors: Preetz
authors: Ryan A
authors: RA
authors: Mesch
authors: Michael J
authors: MJ
authors: Krische
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry; D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D005296:Ferrous Compounds / Q000737:chemistry; D007495:Iridium / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D000075163:Metallocenes; D000432:Methanol / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry; D014961:X-Ray Diffraction
chemical_list: D000438:Alcohols; D000466:Alkadienes; D005296:Ferrous Compounds; D000075163:Metallocenes; D010720:Phosphines; D007495:Iridium; C025947:propadiene; C519379:1,1'-bis(diphenylphosphino)ferrocene; D000432:Methanol