Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published November 26, 2008 | Accepted Version + Supplemental Material
Journal Article Open

Structural features and reactivity of (sparteine)PdCl_2: a model for selectivity in the oxidative kinetic resolution of secondary alcohols


The chiral ligand (−)-sparteine and PdCl_2 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 C1 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 C1 symmetry and Cl− as key features. Further studies of the diastereomers of (−)-sparteine, (−)-α-iso- and (+)-β-isosparteine, in the kinetic resolution showed that these C_2-symmetric counterparts are inferior ligands in this stereoablative reaction

Additional Information

© 2009 American Chemical Society. Received June 27, 2008. This work is dedicated to the memory of Prof. Nelson J. Leonard. The authors thank the NIH-NIGMS (R01 GM65961-01), Bristol-Myers Squibb Co. and the American Chemical Society (graduate fellowship to R.M.T.), Merck Research Laboratories, Abbott Laboratories, Pfizer, Amgen, Boehringer Ingelheim, GlaxoSmithKline, Lilly, and Johnson and Johnson for generous financial support. Mr. Lawrence Henling and Dr. Michael Day are gratefully acknowledged for X-ray crystallographic structural determination.

Attached Files

Accepted Version - nihms91138.pdf

Supplemental Material - Trend2008p182J_Am_Chem_Soc_supp.pdf

Supplemental Material - ja804955e_si_002.cif

Supplemental Material - ja804955e_si_003.cif

Supplemental Material - ja804955e_si_004.cif

Supplemental Material - ja804955e_si_005.cif

Supplemental Material - ja804955e_si_006.cif

Supplemental Material - ja804955e_si_007.cif

Supplemental Material - ja804955e_si_008.cif

Supplemental Material - ja804955e_si_009.cif


Files (7.8 MB)
Name Size Download all
2.3 MB Preview Download
5.2 MB Preview Download
27.6 kB Download
13.7 kB Download
25.2 kB Download
22.8 kB Download
19.2 kB Download
30.1 kB Download
22.9 kB Download
13.9 kB Download

Additional details

August 20, 2023
October 18, 2023