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Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes

Wang, Jane Z. and Benitez, Diego and Tkatchouk, Ekaterina and Goddard, William A., III and Toste, F. Dean (2010) Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes. Journal of the American Chemical Society, 132 (37). pp. 13064-13071. ISSN 0002-7863. PMCID PMC2939907. https://resolver.caltech.edu/CaltechAUTHORS:20101101-140401055

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Abstract

The intermolecular hydroamination of allenes occurs readily with hydrazide nucleophiles, in the presence of 3-12% Ph_3PAuNTf_2. Mechanistic studies have been conducted to establish the resting state of the gold catalyst, the kinetic order of the reaction, the effect of ligand electronics on the overall rate, and the reversibility of the last steps in the catalytic cycle. We have found the overall reaction to be first order in gold and allene and zero order in nucleophile. Our studies suggest that the rate-limiting transition state for the reaction does not involve the nucleophile and that the active catalyst is monomeric in gold(I). Computational studies support an “outersphere” mechanism and predict that a two-step, no intermediate mechanism may be operative. In accord with this mechanistic proposal, the reaction can be accelerated with the use of more electron-deficient phosphine ligands on the gold(I) catalyst.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja105530qDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja105530qPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2939907PubMed CentralArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Toste, F. Dean0000-0001-8018-2198
Additional Information:© 2010 American Chemical Society. Received July 5, 2010. Publication Date (Web): August 25, 2010. We thank the NIHGMS (R01 GM073932) and the Director, Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 for funding and Johnson Mathey for a generous donation of AuCl_3. Z.J.W. thanks the Hertz Foundation for a graduate fellowship. We are also grateful to Dr. Robert Bergman for support during the kinetic studies. Computational facilities were funded by grants from ARO-DURIP and ONR-DURIP.
Funders:
Funding AgencyGrant Number
NIHR01 GM073932
Department of Energy (DOE)DE-AC02-05CH11231
Fannie and John Hertz FoundationUNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:37
PubMed Central ID:PMC2939907
Record Number:CaltechAUTHORS:20101101-140401055
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20101101-140401055
Official Citation:Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes Z. Jane Wang, Diego Benitez, Ekaterina Tkatchouk, William A. Goddard III, F. Dean Toste Journal of the American Chemical Society 2010 132 (37), 13064-13071
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:20624
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:02 Nov 2010 15:31
Last Modified:28 Oct 2019 18:18

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