Asymmetric Synthesis of α-Deuterated α-Amino Acids through Nonenzymatic Transamination Reaction and the Determination of Their Enantiomeric Excesses

• Yoji Tachibana

  The Institute of Physical and Chemical Research

• Makoto Ando

  The Institute of Physical and Chemical Research

• Hiroyoshi Kuzuhara

  The Institute of Physical and Chemical Research

Abstract

Optically active α-deuterated α-amino acids were prepared in methano-d through Zn2+-catalyzed transamination reaction between the chiral pyridoxamine analogs, (R)- or (S)-15-aminomethyl-14-hydroxy-5,5-dimethyl-2,8-dithia[9] (2,5)pyridinophane and various α-keto acids with enantiomeric excesses ranging from 40 to 94%. Aliphatic α-keto acids gave α-deuterated α-amino acids, whereas aromatic ones possessing a methylene group between the carbonyl group (ketone) and the aromatic ring underwent concomitant deuterium substitution at the active methylene group to give the amino acids deuterated at both α- and β-positions of the carboxyl group. The use of the (S)-pyridoxamine analog gave the (R)-deuterated α-amino acids in excess and vice versa. The enatiomeric excesses of the amino acids were determined through the analyses of 1H NMR spectra of the Schiff bases produced by the condensation of the amino acids with the chiral pyridoxal analog, (R)- or (S)-15-formyl-14-hydroxy-2,8-dithia[9](2, 5)pyridinophane. The azomethine protons of the diastereomeric Schiff bases were clearly resolved in the spectrum and their intensities well reflected the amount of the diastereomers.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 56 (12), 3652-3656, 1983-12-01

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1360283694078788608
• NII Article ID: 130001985562
• DOI: 10.1246/bcsj.56.3652
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/56/12/3652/55670235/bcsj.56.3652.pdf
• Data Source:
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  • CiNii Articles