Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 15, Issue 47, Pages 12978-12992Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200902172
Keywords
alcohols; asymmetric catalysis; oxidation; palladium; synthetic methods
Categories
Funding
- NDSEG
- NSF
- University of California TRDRP
- Bristol-Myers Squibb Company
- American Chemical Society Division of Organic Chemistry
- Bristol-Myers Squibb Foundation
- Eli Lilly
- NIH-NIGMS [R01 GM65961-01]
- King Abdullah University of Science and Technology [KUS-11-006-02]
- California Institute of Technology
- A. P. Sloan Foundation
- Dreyfus Foundation
- Research Corporation
- Abbott
- Amgen
- AstraZencca
- Boehringer-Ingelheim
- GlaxoSmithKline
- Johnson and Johnson
- Merck
- Novartis
- Pfizer
- Roche
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM065961] Funding Source: NIH RePORTER
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The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.
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