Iridium-Catalyzed Hydrogen Transfer Reactions

Ourida Saidi, Jonathan M J Williams

Research output: Chapter in Book/Report/Conference proceedingChapter

65 Citations (Scopus)

Abstract

This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.
Original languageEnglish
Title of host publicationIridium Catalysis
Place of PublicationBerlin
PublisherSpringer
Pages77-106
Number of pages30
ISBN (Print)1436-6002
DOIs
Publication statusPublished - 2011

Publication series

NameTopics in Organometallic Chemistry
PublisherSpringer Verlag

Fingerprint

Iridium
Hydrogen
Alcohols
Alkenes
Ketones
Hydrogenation
Carbonyl compounds
formic acid
Imines
Catalysts
Alkylating Agents
Aldehydes
Carbon Dioxide
Amines
Byproducts

Keywords

  • transfer hydrogenation
  • N-alkylation
  • C-alkylation
  • asymmetric transfer hydrogenation
  • oxidation
  • alkenes
  • alcohols
  • reduction
  • imines
  • ketones

Cite this

Saidi, O., & Williams, J. M. J. (2011). Iridium-Catalyzed Hydrogen Transfer Reactions. In Iridium Catalysis (pp. 77-106). (Topics in Organometallic Chemistry). Berlin: Springer. https://doi.org/10.1007/978-3-642-15334-1_4

Iridium-Catalyzed Hydrogen Transfer Reactions. / Saidi, Ourida; Williams, Jonathan M J.

Iridium Catalysis. Berlin : Springer, 2011. p. 77-106 (Topics in Organometallic Chemistry).

Research output: Chapter in Book/Report/Conference proceedingChapter

Saidi, O & Williams, JMJ 2011, Iridium-Catalyzed Hydrogen Transfer Reactions. in Iridium Catalysis. Topics in Organometallic Chemistry, Springer, Berlin, pp. 77-106. https://doi.org/10.1007/978-3-642-15334-1_4
Saidi O, Williams JMJ. Iridium-Catalyzed Hydrogen Transfer Reactions. In Iridium Catalysis. Berlin: Springer. 2011. p. 77-106. (Topics in Organometallic Chemistry). https://doi.org/10.1007/978-3-642-15334-1_4
Saidi, Ourida ; Williams, Jonathan M J. / Iridium-Catalyzed Hydrogen Transfer Reactions. Iridium Catalysis. Berlin : Springer, 2011. pp. 77-106 (Topics in Organometallic Chemistry).
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AB - This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

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