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.
Additional Information
© 2010 Royal Society of Chemistry. Received 6th April 2010, Accepted 5th May 2010. First published on the web 10th June 2010. Electronic supplementary information (ESI) available: Data for new compounds, experimental procedures, and computational data. CCDC reference numbers 772397 and 772398. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0sc00255kAttached Files
Supplemental Material - c0sc00255k.pdf
Supplemental Material - c0sc00255k.txt
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Additional details
- PMCID
- PMC3866133
- Eprint ID
- 73177
- Resolver ID
- CaltechAUTHORS:20170103-130024700
- Created
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2017-01-03Created from EPrint's datestamp field
- Updated
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2021-11-11Created from EPrint's last_modified field