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Chiral N-salicylidene vanadyl carboxylate-catalyzed enantioselective aerobic oxidation of alpha-hydroxy esters and amides

Chiral N-salicylidene vanadyl carboxylate-catalyzed enantioselective aerobic oxidation of alpha-hydroxy esters and amides

Proceedings of the National Academy of Sciences of the United States of America 103(10): 3522-3527

A series of chiral vanadyl carboxylates derived from N-salicylidene-L-alpha-amino acids and vanadyl sulfate has been developed. These configurationally well defined complexes were examined for the kinetic resolution of double- and mono-activated 2 degrees alcohols. The best chiral templates involve the combination of L-tert-leucine and 3,5-di-t-butyl-, 3,5-diphenyl-, or 3,4-dibromo-salicylaldehyde. The resulting vanadyl(V)-methoxide complexes after recrystallization from air-saturated methanol serve as highly enantioselective catalysts for asymmetric aerobic oxidation of alpha-hydroxyl-esters and amides with a diverse array of alpha-, O-, and N-substituents at ambient temperature in toluene. The asymmetric inductions of the oxidation process are in the range of 10 to >100 in terms of selectivity factors (k(rel)) in most instances. The previously undescribed aerobic oxidation protocol is also applicable to the kinetic resolution of C-13 taxol side chain with high selectivity factor (k(rel) = 35). X-ray crystallographic analysis of an adduct between a given vanadyl complex and N-benzyl-mandelamide allows for probing the stereochemical origin of the nearly exclusive asymmetric control in the oxidation process.

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Accession: 048509236

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PMID: 16501046

DOI: 10.1073/pnas.0511021103

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