title: Ruthenium-Catalyzed Transfer Hydrogenation for C-C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs.
abstract: Merging the chemistry of transfer hydrogenation and carbonyl or imine addition, a broad new family of redox-neutral or reductive hydrohydroxyalkylations and hydroaminomethylations have been developed. In these processes, hydrogen redistribution between alcohols and π-unsaturated reactants is accompanied by C-C bond formation, enabling direct conversion of lower alcohols to higher alcohols. Similarly, hydrogen redistribution between amines to π-unsaturated reactants results in direct conversion of lower amines to higher amines. Alternatively, equivalent products of hydrohydroxyalkylation and hydroaminomethylation may be generated through the reaction of carbonyl compounds or imines with π-unsaturated reactants under the conditions of 2-propanol-mediated reductive coupling. Finally, using vicinally dioxygenated reactants, that is, diol, ketols, or diones, successive transfer hydrogenative coupling occurs to generate 2 C-C bonds, resulting in products of formal [4+2] cycloaddition.
authors: Department of Chemistry, University of Texas at Austin, 105 E 24th St., A5300, Austin, TX, 78712-1167, USA.
authors: Felix
authors: F
authors: Perez
authors: Department of Chemistry, University of Texas at Austin, 105 E 24th St., A5300, Austin, TX, 78712-1167, USA.
authors: Susumu
authors: S
authors: Oda
authors: Department of Chemistry, University of Texas at Austin, 105 E 24th St., A5300, Austin, TX, 78712-1167, USA.|Department of Chemistry, University of Nevada, 1664 N Virginia St., Reno, NV, 89557, USA.
authors: Laina M
authors: LM
authors: Geary
authors: Department of Chemistry, University of Texas at Austin, 105 E 24th St., A5300, Austin, TX, 78712-1167, USA. mkrische@mail.utexas.edu.
authors: Michael J
authors: MJ
authors: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000478:Alkylation; D000588:Amines / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D061565:Cycloaddition Reaction; D006865:Hydrogenation; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D000438:Alcohols; D000588:Amines; D056831:Coordination Complexes; D002244:Carbon; D012428:Ruthenium
keywords: Borrowing Hydrogen; C-C Bond Formation; Enantioselective; Ruthenium; Transfer Hydrogenation