期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 130, 期 47, 页码 15957-15966出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja804955e
关键词
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资金
- NIH-NIGMS [R01 GM65961-01]
- Bristol-Myers Squibb Co.
- American Chemical Society
- Merck Research Laboratories
- Abbott Laboratories
- Pfizer
- Amgen
- Boehringer Ingelheim
- GlaxoSmithKIine
- Lilly
- Johnson and Johnson
The chiral ligand (-)-sparteine and PdCl2 catalyze the enantioselective oxidation of secondary alcohols to ketones and thus effect a kinetic resolution. The structural features of sparteine that led to the selectivity observed in the reaction were not clear. Substitution experiments with pyridine derivatives and structural studies of the complexes generated were carried out on (sparteine)PdCl2 and indicated that the C-1 symmetry of (-)-sparteine is essential to the location of substitution at the metal center. Palladium alkoxides were synthesized from secondary alcohols that are relevant steric models for the kinetic resolution. The solid-state structures of the alkoxides also confirmed the results from the pyridine derivative substitution studies. A model for enantioinduction was developed with C-1 symmetry and Cl- as key features. Further studies of the diastereomers of (-)-sparteine, (-)-alpha-iso- and (+)-beta-isosparteine, in the kinetic resolution showed that these C-2-symmetric counterparts are inferior ligands in this stereoablative reaction [Mohr, J. T.; Ebner, D. C.; Stoltz, B. M. Org, Biomol. Chem. 2007, 5,3571-3576].
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