A Convenient Method for Preparation of α-Imino Carboxylic Acid Derivatives and Application to the Asymmetric Synthesis of Unnatural α-Amino Acid Derivative

Tsubasa Inokuma; Takahisa Jichu; Kodai Nishida; Akira Shigenaga; Akira Otaka

doi:10.1248/cpb.c17-00158

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A Convenient Method for Preparation of α-Imino Carboxylic Acid Derivatives and Application to the Asymmetric Synthesis of Unnatural α-Amino Acid Derivative

Tsubasa Inokuma, Takahisa Jichu, Kodai Nishida, Akira Shigenaga, Akira Otaka

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Keywords: α-imino carboxylic acid derivative, heterogeneous oxidant, asymmetric organocatalysis, thiourea, unnatural α-amino acid

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2017 Volume 65 Issue 6 Pages 573-581

DOI https://doi.org/10.1248/cpb.c17-00158

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Abstract

We describe herein a manganese(IV) oxide-mediated oxidation of N-p-methoxyphenyl (PMP)-protected glycine derivatives for the synthesis of α-imino carboxylic acid derivatives. Using this methodology, utilization of unstable glyoxic acid derivatives was avoided. Furthermore, using this methodology we synthesized novel α-imino carboxylic acid derivatives such as α-imino phenyl ester, perfluoroalkyl etsers, imides, and thioester. The asymmetric Mannich reaction of those novel imine derivatives with 1,3-dicarbonyl compound is also described, and the novel α-imino imide gave improved chemical yield and stereoselectivity compared with those obtained by the use of the conventional α-imino ester-type substrate.

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