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Synlett 2012; 23(7): 959-972
DOI: 10.1055/s-0031-1289696
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© Georg Thieme Verlag Stuttgart · New York

Efficient H–D Exchange Reactions Using Heterogeneous Platinum-Group Metal on Carbon–H2–D2O System

Yoshinari Sawama
Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan, Fax: +81(58)2308109   Email: sajiki@gifu-pu.ac.jp
,
Yasunari Monguchi
Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan, Fax: +81(58)2308109   Email: sajiki@gifu-pu.ac.jp
,
Hironao Sajiki*
Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan, Fax: +81(58)2308109   Email: sajiki@gifu-pu.ac.jp
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Publication History

Received: 15 August 2011

Publication Date:
29 March 2012 (online)

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This Account is dedicated to Dr. Yoshifumi Maki, Professor Emeritus at Gifu Pharmaceutical University, on the occasion of his 80th birthday.

Abstract

Deuterium-labeled compounds are widely utilized in various scientific fields. Although the H–D exchange reaction is a straightforward method to produce the deuterated organic compounds, it requires expensive deuterium (D2) gas and/or harsh reaction conditions in conventional methods. This Account summarizes platinum-group metal on carbon (e.g., Pd/C, Pt/C, Ru/C, Rh/C)-catalyzed efficient multi and/or site-selective H–D exchange methods of various compounds including bioactive molecules, such as amino acids, nucleic acids, pharmaceuticals, agrochemicals, and sugars, under neutral and H2-atmospheric conditions in D2O.

1 Introduction and Background

1.1 H–D Exchange Reaction under Acidic or Basic Conditions

1.2 Transition-Metal-Catalyzed H–D Exchange Reaction

1.3 H–D Exchange Reaction under Supercritical State or Hydrothermal Conditions

1.4 Other H–D Exchange Methods

2 Pd/C-Catalyzed H2–D2 Exchange Reaction

3 Site-Selective Benzylic Deuteration under Normal Pressure at Room Temperature

4 Multi H–D Exchange Reaction under Heat Conditions

4.1 Multi H–D Exchange Reaction of Alkyl-Substituted Aromatics

4.2 Multi H–D Exchange Reaction of Heterocyclic Compounds

4.3 Multi H–D Exchange Reaction of Aromatic Nuclei

4.4 Multi H–D Exchange Reaction Using a Mixture of Pd/C and Pt/C or Pd–Pt Hybrid Catalyst

5 H–D Exchange Reaction of Simple Alkanes

6 H–D Exchange Reaction of Alcohols

6.1 The Regioselective H–D Exchange at the α-Position of Aliphatic Alcohols

6.2 The Regio- and Stereoselective Deuterium Labeling of Sugars

7 Conclusion

Key words

H–D exchange - D2 gas - heterogeneous catalysis - platinum-group metals - isotope labeling