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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 involving anti-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.

SUBMITTER: Lalonde RL

PROVIDER: S-EPMC3866133 | biostudies-literature | 2010 Aug

REPOSITORIES: biostudies-literature

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Alkylgold complexes by the intramolecular aminoauration of unactivated alkenes.

Lalonde Rebecca L RL Brenzovich William E WE Benitez Diego D Tkatchouk Ekaterina E Kelley Kotaro K Goddard William A WA Toste F Dean FD

Chemical science 20100801 2

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 involving <i>anti</i>-addition of the nucleophile to a gold-activated alkene, which is verified by DFT analysis of the mechanism. Ligand studie ...[more]

PMID: 24358445

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