Palladium(II)-Catalyzed Exchange and Isomerization Reactions. 17. Exchange of Chiral Allyl Alcohols with Hydroxide, Methoxide, and Phenyl at High [Cl-]. Stereochemistry of the Wacker Reaction

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Journal Title, Volume, Page: 
J. Org. Chem., 64 (21), pp 7745–7750
Year of Publication: 
Othman Hamed
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Patrick M. Henry
Charles Thompson
Preferred Abstract (Original): 
Abstract Image

At high [Cl-] (> 2.0 M), PdCl42- catalyzes the exchange of chiral allylic alcohols with hydroxy, methoxy, and phenyl to give chiral allyl-substituted olefins. With unsymmetrical olefins, isomerization occurs along with exchange. The hydroxyl exchange occurs in aqueous solution while the other exchanges are carried out in methanol solution. At low [Cl-] (0.1 M) oxidation to the corresponding β-hydroxy-, methoxy-, and phenyl-substituted carbonyl compounds occurred. The absolute configurations of the oxidation and exchange products should be the same if the same mode of addition to the Pd(II)-π-complex is operative. The absolute configurations of the oxidation and exchange products for the phenylation reaction were the same, while for hydroxy and methoxy they were different. This result indicates methanol and water must have different stereochemistries of addition at high and low [Cl-]. Thus, previous studies showing anti hydroxypalladation at high [Cl-] are not valid indicators of the stereochemistry at low [Cl-]. If anti addition occurs at high [Cl-], the addition must be syn at low [Cl-].