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Alkylgold complexes by the intramolecular aminoauration of unactivated alkenes

LaLonde, Rebecca L. and Brenzovich, William E., Jr. and Benitez, Diego and Tkatchouk, Ekaterina and Kelley, Kotaro and Goddard, William A., III and Toste, F. Dean (2010) Alkylgold complexes by the intramolecular aminoauration of unactivated alkenes. Chemical Science, 1 (2). pp. 226-233. ISSN 2041-6520. PMCID PMC3866133. https://resolver.caltech.edu/CaltechAUTHORS:20170103-130024700

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c0sc00255kDOIArticle
http://pubs.rsc.org/en/content/articlelanding/2010/sc/c0sc00255kPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3866133/PubMed CentralArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Toste, F. Dean0000-0001-8018-2198
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/c0sc00255k
Issue or Number:2
PubMed Central ID:PMC3866133
Record Number:CaltechAUTHORS:20170103-130024700
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170103-130024700
Official Citation:Alkylgold complexes by the intramolecular aminoauration of unactivated alkenes Rebecca L. LaLonde, William E. Brenzovich, Jr., Diego Benitez, Ekaterina Tkatchouk, Kotaro Kelley, William A. Goddard, III and F. Dean Toste Chem. Sci., 2010,1, 226-233 DOI: 10.1039/C0SC00255K
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73177
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:03 Jan 2017 21:18
Last Modified:28 Oct 2019 18:19

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