title: Alkylgold complexes by the intramolecular aminoauration of unactivated alkenes.
abstract: Alkylgold(I) complexes were formed from the gold(I)-promoted intramolecular addition of various amine nucleophiles to alkenes. These experiments provide the first direct experimental evidence for the elementary step of gold-promoted nucleophilic addition to an alkene. Deuterium-labeling studies and X-ray crystal structures provide support for a mechanism involvinganti-addition of the nucleophile to a gold-activated alkene, which is verified by DFT analysis of the mechanism. Ligand studies indicate that the rate of aminoauration can be drastically increased by use of electron-poor arylphosphines, which are also shown to be favored in ligand exchange experiments. Attempts at protodeauration lead only to recovery of the starting olefins, though the gold can be removed under reducing conditions to provide the purported hydroamination products.
authors.affiliation: Department of Chemistry, University of California Berkeley, Berkeley, CA, USA. ; Tel: +1 510-642-2850.
authors.forename: Rebecca L
authors.initials: RL
authors.lastname: Lalonde
authors.affiliation: Department of Chemistry, University of California Berkeley, Berkeley, CA, USA. ; Tel: +1 510-642-2850.
authors.forename: William E
authors.initials: WE
authors.lastname: Brenzovich
authors.affiliation: Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA.
authors.forename: Diego
authors.initials: D
authors.lastname: Benitez
authors.affiliation: Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA.
authors.forename: Ekaterina
authors.initials: E
authors.lastname: Tkatchouk
authors.affiliation: Department of Chemistry, University of California Berkeley, Berkeley, CA, USA. ; Tel: +1 510-642-2850.
authors.forename: Kotaro
authors.initials: K
authors.lastname: Kelley
authors.affiliation: Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA.
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.affiliation: Department of Chemistry, University of California Berkeley, Berkeley, CA, USA. ; Tel: +1 510-642-2850.
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste