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 - D
2 gas - heterogeneous catalysis - platinum-group metals - isotope labeling
