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Two Metals Are Better Than One in the Gold Catalyzed Oxidative Heteroarylation of Alkenes

Tkatchouk, Ekaterina and Mankad, Neal P. and Benitez, Diego and Goddard, William A., III and Toste, F. Dean (2011) Two Metals Are Better Than One in the Gold Catalyzed Oxidative Heteroarylation of Alkenes. Journal of the American Chemical Society, 133 (36). pp. 14293-14300. ISSN 0002-7863. PMCID PMC3168709. https://resolver.caltech.edu/CaltechAUTHORS:20111018-095440280

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Abstract

We present a detailed study of the mechanism for oxidative heteroarylation, based on DFT calculations and experimental observations. We propose binuclear Au(II)–Au(II) complexes to be key intermediates in the mechanism for gold catalyzed oxidative heteroarylation. The reaction is thought to proceed via a gold redox cycle involving initial oxidation of Au(I) to binuclear Au(II)–Au(II) complexes by Selectfluor, followed by heteroauration and reductive elimination. While it is tempting to invoke a transmetalation/reductive elimination mechanism similar to that proposed for other transition metal complexes, experimental and DFT studies suggest that the key C–C bond forming reaction occurs via a bimolecular reductive elimination process (devoid of transmetalation). In addition, the stereochemistry of the elimination step was determined experimentally to proceed with complete retention. Ligand and halide effects played an important role in the development and optimization of the catalyst; our data provides an explanation for the ligand effects observed experimentally, useful for future catalyst development. Cyclic voltammetry data is presented that supports redox synergy of the Au···Au aurophilic interaction. The monometallic reductive elimination from mononuclear Au(III) complexes is also studied from which we can predict a ~ 15 kcal/mol advantage for bimetallic reductive elimination.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja2012627DOIArticle
http://pubs.acs.org/doi/full/10.1021/ja2012627PublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3168709PubMed CentralArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Toste, F. Dean0000-0001-8018-2198
Additional Information:© 2011 American Chemical Society. Received: February 10, 2011. Publication Date (Web): August 23, 2011. This material is based upon work supported as part of the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001298. Computational facilities were funded by grants from ARO-DURIP and ONR-DURIP. N.P.M. was supported by an NIH Kirchstein-NRSA postdoctoral fellowship. Prof. Chris Chang provided access to a potentiostat for cyclic voltammetry measurements.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0001298
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
NIH Postdoctoral FellowshipUNSPECIFIED
Issue or Number:36
PubMed Central ID:PMC3168709
Record Number:CaltechAUTHORS:20111018-095440280
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20111018-095440280
Official Citation:Two Metals Are Better Than One in the Gold Catalyzed Oxidative Heteroarylation of Alkenes Ekaterina Tkatchouk, Neal P. Mankad, Diego Benitez, William A. Goddard III, and F. Dean Toste Journal of the American Chemical Society 2011 133 (36), 14293-14300
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:27274
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:18 Oct 2011 17:51
Last Modified:28 Oct 2019 18:17

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