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Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates

Wolfe, John P. and Tomori, Hiroshi and Sadighi, Joseph P. and Yin, Jingjun and Buchwald, Stephen L. (2000) Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates. Journal of Organic Chemistry, 65 (4). pp. 1158-1174. ISSN 0022-3263. https://resolver.caltech.edu/CaltechAUTHORS:20170427-084536101

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Abstract

Palladium complexes supported by (o-biphenyl)P(t-Bu)_2 (3) or (o-biphenyl)PCy_2 (4) are efficient catalysts for the catalytic amination of a wide variety of aryl halides and triflates. Use of ligand 3 allows for the room-temperature catalytic amination of many aryl chloride, bromide, and triflate substrates, while ligand 4 is effective for the amination of functionalized substrates or reactions of acyclic secondary amines. The catalysts perform well for a large number of different substrate combinations at 80−110 °C, including chloropyridines and functionalized aryl halides and triflates using 0.5−1.0 mol % Pd; some reactions proceed efficiently at low catalyst levels (0.05 mol % Pd). These ligands are effective for almost all substrate combinations that have been previously reported with various other ligands, and they represent the most generally effective catalyst system reported to date. Ligands 3 and 4 are air-stable, crystalline solids that are commercially available. Their effectiveness is believed to be due to a combination of steric and electronic properties that promote oxidative addition, Pd−N bond formation, and reductive elimination.


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http://dx.doi.org/10.1021/jo991699yDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jo991699yPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jo991699yPublisherSupporting Information
Additional Information:© 2000 American Chemical Society. Received 29 October 1999. Published online 2 February 2000. Published in print 1 February 2000. We thank the National Institutes of Health (GM 58160), the National Cancer Institute (training grant NCI CI T32CA09112), and the Office of Naval Research for financial support of this work. We also acknowledge Pfizer, Merck, and Novartis for additional unrestricted support. J.P.W. is grateful for a fellowship from the Organic Division of the American Chemical Society sponsored by Schering-Plough. H.T. thanks Sankyo Co. Ltd. for support. We thank Mr. John Kowalski for conducting initial experiments on the room-temperature catalytic amination of aryl bromides using ligand 3.
Funders:
Funding AgencyGrant Number
NIHGM58160
NIH Predoctoral FellowshipT32CA09112
Office of Naval Research (ONR)UNSPECIFIED
PfizerUNSPECIFIED
MerckUNSPECIFIED
NovartisUNSPECIFIED
American Chemical Society Organic DivisionUNSPECIFIED
Sankyo Co. Ltd.UNSPECIFIED
Issue or Number:4
Record Number:CaltechAUTHORS:20170427-084536101
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170427-084536101
Official Citation:Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates John P. Wolfe, Hiroshi Tomori, Joseph P. Sadighi, Jingjun Yin, and Stephen L. Buchwald The Journal of Organic Chemistry 2000 65 (4), 1158-1174 DOI: 10.1021/jo991699y
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76983
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:27 Apr 2017 16:11
Last Modified:03 Oct 2019 17:52

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