Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates
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.
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.Attached Files
Supplemental Material - jo991699y_s.pdf
Files
Name | Size | Download all |
---|---|---|
md5:340921dc3118cd82a76aef00f6242aa9
|
602.4 kB | Preview Download |
Additional details
- Eprint ID
- 76983
- Resolver ID
- CaltechAUTHORS:20170427-084536101
- GM58160
- NIH
- T32CA09112
- NIH Predoctoral Fellowship
- Office of Naval Research (ONR)
- Pfizer
- Merck
- Novartis
- American Chemical Society Organic Division
- Sankyo Co. Ltd.
- Created
-
2017-04-27Created from EPrint's datestamp field
- Updated
-
2021-11-15Created from EPrint's last_modified field