Glyoxylic Acid versus Ethyl Glyoxylate for the Aqueous Enantio­selective Synthesis of α-Hydroxy-γ-Keto Acids and Esters by the N-Tosyl-(Sa)-binam-l-prolinamide-Organocatalyzed Aldol Reaction

Fernando J. N. Moles; Gabriela Guillena; Carmen Nájera; Enrique Gómez-Bengoa

doi:10.1055/s-0034-1379546

Synthesis, Table of Contents

Synthesis 2015; 47(04): 549-561
DOI: 10.1055/s-0034-1379546

paper

Glyoxylic Acid versus Ethyl Glyoxylate for the Aqueous Enantioselective Synthesis of α-Hydroxy-γ-Keto Acids and Esters by the N-Tosyl-(S _a)-binam-l-prolinamide-Organocatalyzed Aldol Reaction

Fernando J. N. Moles

^aDepartamento de Química Orgánica and Instituto de Síntesis Orgánica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain Fax: +34(96)5903549 Email: gabriela.guillena@ua.es Email: cnajera@ua.es

,

Gabriela Guillena*

^aDepartamento de Química Orgánica and Instituto de Síntesis Orgánica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain Fax: +34(96)5903549 Email: gabriela.guillena@ua.es Email: cnajera@ua.es

,

Carmen Nájera*

^aDepartamento de Química Orgánica and Instituto de Síntesis Orgánica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain Fax: +34(96)5903549 Email: gabriela.guillena@ua.es Email: cnajera@ua.es

,

Enrique Gómez-Bengoa*

^bDepartamento de Química Orgánica I, Universidad del País Vasco, Apdo. 1072, 20080 San Sebastián, Spain Email: enrique.gomez@ehu.es

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Abstract

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Abstract

N-Tosyl-(S _a)-binam-l-prolinamide is an efficient catalyst for the aqueous aldol reaction between ketones and glyoxylic acid, as the monohydrate or as an aqueous solution, or a 50% toluene solution of ethyl glyoxylate. These reactions led to the formation of chiral α-hydroxy-γ-keto carboxylic acids and esters in high levels of diastereo- and enantioselectivities (up to 97% ee), providing mainly anti aldol products. Only cyclopentanone and cyclohexane-1,4-dione afforded an almost 1:1 mixture of the syn/anti-diastereoisomers; however, the reaction between 4-phenylcyclohexanone and ethyl glyoxylate gave the corresponding syn,syn-product as the major diastereoisomer.

Key words

aldol reaction - organocatalysis - glyoxylic acid - prolinamide - water

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References

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Supplementary Material

Supporting Information

Glyoxylic Acid versus Ethyl Glyoxylate for the Aqueous Enantio­selective Synthesis of α-Hydroxy-γ-Keto Acids and Esters by the N-Tosyl-(S a)-binam-l-prolinamide-Organocatalyzed Aldol Reaction

Glyoxylic Acid versus Ethyl Glyoxylate for the Aqueous Enantioselective Synthesis of α-Hydroxy-γ-Keto Acids and Esters by the N-Tosyl-(S _a)-binam-l-prolinamide-Organocatalyzed Aldol Reaction