Action of L-aminoacylase and L-amino acid oxidase on 2-amino-3- methylpent-4-enoic acid [Δ(4)-dehydroisoleucine and alloisoleucine] stereoisomers

An alternative route to a stereochemically pure compound and the application to the synthesis of (R)-2-methylbutan-1-ol

Mikio Bakke, Hiromichi Ohta, Uli Kazmaier, Takeshi Sugai

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The action of L-aminoacylase and L-amino acid oxidase on the stereoisomers of 2-amino-3-methylpent-4-enoic acid was examined, to secure stereochemically pure compounds related to L-alloisoleucine. A scalemic mixture [(2S,3R)- (90.0%), (2S,3S)(3.2%), (2R,3S)- (5.9%), (2R,3R)- (0.9%)] of the N-trifluoroacetyl derivatives of the title compound, which was prepared by an asymmetric Claisen rearrangement, was submitted to Aspergillus L-aminoacylase-catalyzed hydrolysis. Only the (2S,3R)- and (2S,3S)isomers were hydrolyzed to give the corresponding amino acids. The subsequent treatment of these isomers with Crotalus adamanteus L-amino acid oxidase afforded the pure (2S,3R)-isomer, related to L-alloisoleucine, in more than 99% stereochemically pure form. Moreover, the product was converted to L- alloisoleucine and (R)-2-methylbutan-1-ol via a chemoenzymatic procedure.

Original languageEnglish
Pages (from-to)1671-1677
Number of pages7
JournalSynthesis
Issue number9
Publication statusPublished - 1999

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L-Amino Acid Oxidase
Stereoisomerism
Isoleucine
Isomers
Amino acids
Acids
Aspergillus
Hydrolysis
Derivatives
Amino Acids
aminoacylase I
Oxidoreductases

Keywords

  • (R)-2-methylbutan-1-ol
  • Chelation-controlled enolate Claisen rearrangement
  • L-alloisoleucine
  • L-amino acids oxidase
  • L-aminoacylase

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Action of L-aminoacylase and L-amino acid oxidase on 2-amino-3- methylpent-4-enoic acid [Δ(4)-dehydroisoleucine and alloisoleucine] stereoisomers: An alternative route to a stereochemically pure compound and the application to the synthesis of (R)-2-methylbutan-1-ol",
abstract = "The action of L-aminoacylase and L-amino acid oxidase on the stereoisomers of 2-amino-3-methylpent-4-enoic acid was examined, to secure stereochemically pure compounds related to L-alloisoleucine. A scalemic mixture [(2S,3R)- (90.0{\%}), (2S,3S)(3.2{\%}), (2R,3S)- (5.9{\%}), (2R,3R)- (0.9{\%})] of the N-trifluoroacetyl derivatives of the title compound, which was prepared by an asymmetric Claisen rearrangement, was submitted to Aspergillus L-aminoacylase-catalyzed hydrolysis. Only the (2S,3R)- and (2S,3S)isomers were hydrolyzed to give the corresponding amino acids. The subsequent treatment of these isomers with Crotalus adamanteus L-amino acid oxidase afforded the pure (2S,3R)-isomer, related to L-alloisoleucine, in more than 99{\%} stereochemically pure form. Moreover, the product was converted to L- alloisoleucine and (R)-2-methylbutan-1-ol via a chemoenzymatic procedure.",
keywords = "(R)-2-methylbutan-1-ol, Chelation-controlled enolate Claisen rearrangement, L-alloisoleucine, L-amino acids oxidase, L-aminoacylase",
author = "Mikio Bakke and Hiromichi Ohta and Uli Kazmaier and Takeshi Sugai",
year = "1999",
language = "English",
pages = "1671--1677",
journal = "Synthesis (Germany)",
issn = "0039-7881",
publisher = "Georg Thieme Verlag",
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TY - JOUR

T1 - Action of L-aminoacylase and L-amino acid oxidase on 2-amino-3- methylpent-4-enoic acid [Δ(4)-dehydroisoleucine and alloisoleucine] stereoisomers

T2 - An alternative route to a stereochemically pure compound and the application to the synthesis of (R)-2-methylbutan-1-ol

AU - Bakke, Mikio

AU - Ohta, Hiromichi

AU - Kazmaier, Uli

AU - Sugai, Takeshi

PY - 1999

Y1 - 1999

N2 - The action of L-aminoacylase and L-amino acid oxidase on the stereoisomers of 2-amino-3-methylpent-4-enoic acid was examined, to secure stereochemically pure compounds related to L-alloisoleucine. A scalemic mixture [(2S,3R)- (90.0%), (2S,3S)(3.2%), (2R,3S)- (5.9%), (2R,3R)- (0.9%)] of the N-trifluoroacetyl derivatives of the title compound, which was prepared by an asymmetric Claisen rearrangement, was submitted to Aspergillus L-aminoacylase-catalyzed hydrolysis. Only the (2S,3R)- and (2S,3S)isomers were hydrolyzed to give the corresponding amino acids. The subsequent treatment of these isomers with Crotalus adamanteus L-amino acid oxidase afforded the pure (2S,3R)-isomer, related to L-alloisoleucine, in more than 99% stereochemically pure form. Moreover, the product was converted to L- alloisoleucine and (R)-2-methylbutan-1-ol via a chemoenzymatic procedure.

AB - The action of L-aminoacylase and L-amino acid oxidase on the stereoisomers of 2-amino-3-methylpent-4-enoic acid was examined, to secure stereochemically pure compounds related to L-alloisoleucine. A scalemic mixture [(2S,3R)- (90.0%), (2S,3S)(3.2%), (2R,3S)- (5.9%), (2R,3R)- (0.9%)] of the N-trifluoroacetyl derivatives of the title compound, which was prepared by an asymmetric Claisen rearrangement, was submitted to Aspergillus L-aminoacylase-catalyzed hydrolysis. Only the (2S,3R)- and (2S,3S)isomers were hydrolyzed to give the corresponding amino acids. The subsequent treatment of these isomers with Crotalus adamanteus L-amino acid oxidase afforded the pure (2S,3R)-isomer, related to L-alloisoleucine, in more than 99% stereochemically pure form. Moreover, the product was converted to L- alloisoleucine and (R)-2-methylbutan-1-ol via a chemoenzymatic procedure.

KW - (R)-2-methylbutan-1-ol

KW - Chelation-controlled enolate Claisen rearrangement

KW - L-alloisoleucine

KW - L-amino acids oxidase

KW - L-aminoacylase

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