Michael addition reactions between chiral equivalents of a nucleophilic glycine and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general method for efficient preparation of β-substituted pyroglutamic acids. Case of topographically controlled stereoselectivity

Vadim A. Soloshonok, Chaozhong Cai, Takeshi Yamada, Hisanori Ueki, Yasufumi Ohfune, Victor J Hruby

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Abstract

This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o[N-(N- benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3- oxazolidin-2-ones as a general and synthetically efficient approach to β-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) Stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust Stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involing a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various β-substituted pyroglutamic acids and related compounds.

Original languageEnglish (US)
Pages (from-to)15296-15303
Number of pages8
JournalJournal of the American Chemical Society
Volume127
Issue number43
DOIs
StatePublished - Nov 2 2005

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Pyrrolidonecarboxylic Acid
Oxazolidinones
Stereoselectivity
Addition reactions
Glycine
Reaction rates
Amino acids
Acids
Schiff Bases
Chirality
Enzymes
Temperature
Substrates
benzophenone

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{29e2297c6663444a90789024fbef044b,
title = "Michael addition reactions between chiral equivalents of a nucleophilic glycine and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general method for efficient preparation of β-substituted pyroglutamic acids. Case of topographically controlled stereoselectivity",
abstract = "This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o[N-(N- benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3- oxazolidin-2-ones as a general and synthetically efficient approach to β-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98{\%} diastereomeric excess (de)) Stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98{\%}) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust Stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involing a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various β-substituted pyroglutamic acids and related compounds.",
author = "Soloshonok, {Vadim A.} and Chaozhong Cai and Takeshi Yamada and Hisanori Ueki and Yasufumi Ohfune and Hruby, {Victor J}",
year = "2005",
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TY - JOUR

T1 - Michael addition reactions between chiral equivalents of a nucleophilic glycine and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general method for efficient preparation of β-substituted pyroglutamic acids. Case of topographically controlled stereoselectivity

AU - Soloshonok, Vadim A.

AU - Cai, Chaozhong

AU - Yamada, Takeshi

AU - Ueki, Hisanori

AU - Ohfune, Yasufumi

AU - Hruby, Victor J

PY - 2005/11/2

Y1 - 2005/11/2

N2 - This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o[N-(N- benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3- oxazolidin-2-ones as a general and synthetically efficient approach to β-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) Stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust Stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involing a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various β-substituted pyroglutamic acids and related compounds.

AB - This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o[N-(N- benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3- oxazolidin-2-ones as a general and synthetically efficient approach to β-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) Stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust Stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involing a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various β-substituted pyroglutamic acids and related compounds.

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