Highly efficient D 2 generation by dehydrogenation of formic acid in D 2O through H +/D + exchange on an iridium catalyst: Application to the synthesis of deuterated compounds by transfer deuterogenation

Wan Hui Wang, Jonathan F. Hull, James T. Muckerman, Etsuko Fujita, Takuji Hirose, Yuichiro Himeda

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Deuterated compounds have received increasing attention in both academia and industrial fields. However, preparations of these compounds are limited for both economic and practical reasons. Herein, convenient generation of deuterium gas (D 2) and the preparation of deuterated compounds on a laboratory scale are demonstrated by using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'-bipyridine. The "umpolung" (i.e., reversal of polarity) of a hydrogen atom of water was achieved in consecutive reactions, that is, a cationic H +/D + exchange reaction and anionic hydride or deuteride transfer, under mild conditions. Selective D 2 evolution (purity up to 89%) was achieved by using HCO 2H as an electron source and D 2O as a deuterium source; a rhodium analogue provided HD gas (98%) under similar conditions. Furthermore, pressurized D 2 (98%) without CO gas was generated by using DCO 2D in D 2O in a glass autoclave. Transfer deuterogenation of ketones gave α-deuterated alcohols with almost quantitative yields and high deuterium content by using HCO 2H in D 2O. Mechanistic studies show that the H +/D + exchange reaction in the iridium hydride complex was much faster than β-elimination and hydride (deuteride) transfer. Cheap D 2 gas! Convenient generation of deuterium gas (D 2) and preparation of deuterated compounds on a laboratory scale are demonstrated using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'- bipyridine (see scheme). The "umpolung" of a hydrogen atom of water was achieved in consecutive reactions (cationic H +/D + exchange reaction and anionic hydride (deuteride) transfer) under mild conditions.

Original languageEnglish
Pages (from-to)9397-9404
Number of pages8
JournalChemistry - A European Journal
Volume18
Issue number30
DOIs
Publication statusPublished - Jul 23 2012

Keywords

  • deuterium
  • iridium
  • isotopic exchange
  • reaction mechanism
  • synthetic methods
  • umpolung

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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