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 Muckerman, Etsuko Fujita, Takuji Hirose, Yuichiro Himeda

Research output: Contribution to journalArticle

30 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

Fingerprint

formic acid
Iridium
Formic acid
Dehydrogenation
Deuterium
Hydrides
Gases
Catalysts
Hydrogen
2,2'-Dipyridyl
Electron sources
Atoms
Rhodium
Water
Autoclaves
Carbon Monoxide
Ketones
Alcohols
Glass
Economics

Keywords

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

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{c67e026a135e459f9a728a1a51d77976,
title = "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",
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.",
keywords = "deuterium, iridium, isotopic exchange, reaction mechanism, synthetic methods, umpolung",
author = "Wang, {Wan Hui} and Hull, {Jonathan F.} and James Muckerman and Etsuko Fujita and Takuji Hirose and Yuichiro Himeda",
year = "2012",
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T1 - Highly efficient D 2 generation by dehydrogenation of formic acid in D 2O through H +/D + exchange on an iridium catalyst

T2 - Application to the synthesis of deuterated compounds by transfer deuterogenation

AU - Wang, Wan Hui

AU - Hull, Jonathan F.

AU - Muckerman, James

AU - Fujita, Etsuko

AU - Hirose, Takuji

AU - Himeda, Yuichiro

PY - 2012/7/23

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AB - 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.

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KW - isotopic exchange

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KW - synthetic methods

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