title: Direct catalytic addition of alkylnitriles to aldehydes by transition-metal/NHC complexes.
abstract: Direct catalytic addition of alkylnitriles to aldehydes allows for an atom-economical access to β-hydroxynitriles under proton transfer conditions. Direct use of alkylnitriles as pronucleophiles has been hampered due to their low acidity resulting in an inability to generate α-cyano carbanions in a catalytic manner. A transition metal/N-heterocyclic carbene (NHC) complex prepared from [{Rh(OMe)(cod)}2] and an imidazolium-based carbene was identified as an effective catalyst to promote the reaction with as little as 1.25 mol% of catalyst loading. The corresponding Rh complex, derived from chiral triazolium salt, rendered the reaction enantioselective, albeit with moderate enantioselectivity.
authors.affiliation: Institute of Microbial Chemistry (BIKAKEN), Tokyo, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo 141-0021 (Japan).
authors.forename: Devarajulu
authors.initials: D
authors.lastname: Sureshkumar
authors.forename: Venkataraman
authors.initials: V
authors.lastname: Ganesh
authors.forename: Naoya
authors.initials: N
authors.lastname: Kumagai
authors.forename: Masakatsu
authors.initials: M
authors.lastname: Shibasaki
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D056831:Coordination Complexes; D006571:Heterocyclic Compounds; D007093:Imidazoles; D007477:Ions; D008670:Metals; D009570:Nitriles; D028561:Transition Elements; C030011:carbene; D012238:Rhodium; D008697:Methane
keywords: N-heterocyclic carbenes; alkylnitriles; asymmetric catalysis; cooperative catalysis; rhodium