title: Mechanism of the [(NHC)Au(I)]-catalyzed rearrangement of allylic acetates. A DFT study.
abstract: The DFT study of the mechanism of the rearrangement of H(2)C=CHC(CH(3))OCOCH(3) to (CH(3))(H)C=CHCH(2)OCOCH(3) catalyzed by [(NHC)Au](+) (NHC = N-heterocyclic carbene) shows that a low energy path exists, with a barrier of 14.2 kcal x mol(-1), going through a six-membered ring acetoxonium intermediate and where gold coordinates one of the carbon atoms in the alkene system. The qualitative features of the mechanism are not affected by the introduction of other NHC ligands, counterions, or solvation effects.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans, 16, 43007 Tarragona, Catalonia, Spain.
authors.forename: Christophe
authors.initials: C
authors.lastname: Gourlaouen
authors.forename: Nicolas
authors.initials: N
authors.lastname: Marion
authors.forename: Steven P
authors.initials: SP
authors.lastname: Nolan
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D006046:Gold / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D050607:Organogold Compounds / Q000737:chemistry*
chemical_list: D000085:Acetates; D000498:Allyl Compounds; D006571:Heterocyclic Compounds; D050607:Organogold Compounds; C030011:carbene; D006046:Gold; D008697:Methane