Chapter 21. Biochemistry of Enamines

  1. Zvi Rappoport Professor
  1. Frank Jordan

Published Online: 20 JUL 2004

DOI: 10.1002/0470024763.ch21

Enamines (1994)

Enamines (1994)

How to Cite

Jordan, F. (2004) Biochemistry of Enamines, in Enamines (1994) (ed Z. Rappoport), John Wiley & Sons, Ltd, Chichester, UK. doi: 10.1002/0470024763.ch21

Editor Information

  1. The Hebrew University, Jerusalem, Israel

Author Information

  1. Department of Chemistry, Rutgers, the State University of New Jersey, Newark, New Jersey, USA

Publication History

  1. Published Online: 20 JUL 2004
  2. Published Print: 31 AUG 1994

Book Series:

  1. PATAI'S Chemistry of Functional Groups

Book Series Editors:

  1. Saul Patai and
  2. Zvi Rappoport

Series Editor Information

  1. The Hebrew University, Jerusalem, Israel

ISBN Information

Print ISBN: 9780471933397

Online ISBN: 9780470024768

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Summary

This chapter contains sections titled:

  • Introduction

  • Enamines in Thiamin Diphosphate-dependent Reactions

    • Chemical Models of Enamine Reactivity

      • Structure in Solution

      • Acidity of Enamine Precursor 2-alkylthiazolium Salts at C2α in DMSO

      • Acidity of Enamine Precursor 2-alkylthiazolium Salts at C2α

      • Kinetics of Proton Transfer to and from C2α in 2-alkylthiazolium Salts

      • Redox Chemistry of the Enamine

        • Indirect Evidence for Oxidative Enamine Trapping

        • Direct Electrochemical Oxidation Behavior of Enamines

      • Condensation Reactions of the Enamines at C2α

    • Enzymatic Reactions of Thiamin-bound Enamines in Decarboxylases

      • Generation and Identification of Enamines Bound to Pyruvate Decarboxylase

      • Visible Spectroscopic Properties of Enzyme-bound Enamines

      • Redox Properties of Enzyme-bound Enamines

        • Evidence for 2-acylthiamin Diphosphate Intermediates on α-keto Acid Dehydrogenases

        • Oxidation of the Thiamin-bound Enamines on Pyruvate Decarboxylase

        • Redox Reactions Resulting from Enamines Derived from Halopyruvate Analogs

        • Trapping the Enzyme-bound Enamines by Flavins

        • Adventitious Enamine Oxidation by Dioxygen

      • Kinetic Competence of Enzyme-bound Enamines

      • Stereochemical Behavior of Enzyme-bound Enamines

      • Are Enamine Mimics General Transition-state Analogs for Thiamin Diphosphate-dependent Enzymes?

      • Possible Role of Thiamin Diphosphate-dependent Enzymes in Enamine Stabilization

    • The Reaction of Transketolase

  • Enamines in Schiff Base Enzymes

    • Lysine-dependent ‘Schiff Base’ Enzymes

      • Acetoacetate Decarboxylation

      • Class I Aldolases

    • Pyridoxal-dependent Enzymes

    • Pyruvyl-dependent Decarboxylations

  • Enamines in Oxidation–reduction Cofactors

    • Flavin Cofactors

    • Nicotinamide Cofactors

    • Biopterin Cofactors

  • Enamines in Tryptophan Metabolism

  • Recent Applications of Biochemical Enamines

    • Enamines as Mechanism-based Enzyme Inhibitors

    • Chiral Synthesis with Enzymes That Utilize Enamines Intermediates

  • Acknowledgments

  • References