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Palladium-catalyzed chemo- and enantioselective oxidation of allylic esters and carbonates.

ABSTRACT: The palladium-catalyzed oxidation of allylic esters and carbonates using a novel potassium nitronate has been developed. This method is highly chemoselective, leaving other esters, alcohols, thioethers, and amines undisturbed. The oxidation can be operated in two modes: an achiral mode, using either PPh3 or rac-2 as ligand, or a chiral and highly enantioselective mode, using 2 as ligand. The oxidative enantioselective desymmetrization of meso bis-esters provides a significantly shorter method to arrive at commonly used synthetic intermediates compared to other strategies. Highly efficient kinetic resolution is also possible using this methodology.

SUBMITTER: Trost BM

PROVIDER: S-EPMC2531164 | biostudies-literature | 2006 Mar

REPOSITORIES: biostudies-literature

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Palladium-catalyzed chemo- and enantioselective oxidation of allylic esters and carbonates.

Trost Barry M BM Richardson Jeffery J Yong Kelvin K

Journal of the American Chemical Society 20060301 8

The palladium-catalyzed oxidation of allylic esters and carbonates using a novel potassium nitronate has been developed. This method is highly chemoselective, leaving other esters, alcohols, thioethers, and amines undisturbed. The oxidation can be operated in two modes: an achiral mode, using either PPh3 or rac-2 as ligand, or a chiral and highly enantioselective mode, using 2 as ligand. The oxidative enantioselective desymmetrization of meso bis-esters provides a significantly shorter method to ...[more]

PMID: 16492030

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