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Gathergood N, Juhl K, Poulsen TB, et al. Direct catalytic asymmetric aldol reactions of pyruvates: scope and mechanism. Org Biomol Chem. 2004;2(7):1077-85doi: 10.1039/b316092k.
Gathergood, N., Juhl, K., Poulsen, T. B., Thordrup, K., & Jørgensen, K. A. (2004). Direct catalytic asymmetric aldol reactions of pyruvates: scope and mechanism. Organic & biomolecular chemistry, 2(7), 1077-85. https://doi.org/10.1039/b316092k
Gathergood, Nicholas, et al. "Direct catalytic asymmetric aldol reactions of pyruvates: scope and mechanism." Organic & biomolecular chemistry vol. 2,7 (2004): 1077-85. doi: https://doi.org/10.1039/b316092k
Gathergood N, Juhl K, Poulsen TB, Thordrup K, Jørgensen KA. Direct catalytic asymmetric aldol reactions of pyruvates: scope and mechanism. Org Biomol Chem. 2004 Apr 07;2(7):1077-85. doi: 10.1039/b316092k. Epub 2004 Mar 09. PMID: 15034632.
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Org Biomol Chem. 2004 Apr 07;2(7):1077-85. doi: 10.1039/b316092k. Epub 2004 Mar 09.

Direct catalytic asymmetric aldol reactions of pyruvates: scope and mechanism.

Organic & biomolecular chemistry

Nicholas Gathergood, Karsten Juhl, Thomas B Poulsen, Karl Thordrup, Karl Anker Jørgensen

Affiliations

  1. Danish National Research Foundation: Center for Catalysis, Department of Chemistry, Aarhus University, DK-8000, Aarhus C, Denmark.

PMID: 15034632 DOI: 10.1039/b316092k

Abstract

The direct aldol reaction of 2-ketoesters catalyzed by chiral bisoxazoline copper(II) complexes has been investigated. First the direct homo-aldol reaction of ethyl pyruvate is reported which proceeds to give diethyl 2-hydroxy-2-methyl-4-oxoglutarate. This was isolated as the more stable optically active isotetronic acid in good yield and enantiomeric excess in the absence of bases such as amines. Detailed investigations of the use of different chiral Lewis acids as the catalyst, amines, ratios of chiral bisoxazoline copper(II) salts:amine, and solvents gave up to 96% ee of the isotetronic acid. Then the reaction was extended to a cross-aldol reaction of various 2-ketoesters with activated carbonyl compounds to give the cross-aldol adduct with excellent enantiomeric excess. Furthermore, the synthesis of the isotetronic acids was investigated from these cross-aldol adducts giving important information about the formation of the stereogenic centers during the aldol reaction. Based on the absolute configuration of the homo-aldol adduct the mechanism for the aldol reaction is discussed.

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