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 http://resolver.caltech.edu/CaltechAUTHORS:20101101-140401055
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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.
|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 AuCl3. 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.|
|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|
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|Deposited By:||Ruth Sustaita|
|Deposited On:||02 Nov 2010 15:31|
|Last Modified:||26 Dec 2012 12:35|
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