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Synlett 2005(4): 560-571  
DOI: 10.1055/s-2005-862381
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Cp*Ir Complex-Catalyzed Hydrogen Transfer Reactions Directed toward Environmentally Benign Organic Synthesis

Ken-ichi Fujita, Ryohei Yamaguchi*
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
Fax: +81(75)7536634; e-Mail: fujitak@kagaku.mbox.media.kyoto-u.ac.jp; e-Mail: yama@kagaku.mbox.media.kyoto-u.ac.jp;
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Publication History

Received 1 October 2004
Publication Date:
22 February 2005 (online)

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Abstract

Catalytic activity of Cp*Ir complexes toward hydrogen transfer reactions are discussed. Three different types of reactions have been developed. The first is Oppenauer-type oxidation of alcohols. This reaction proceeds under quite mild conditions (room temperature in acetone) catalyzed by [Cp*IrCl2]2/K2CO3, and both primary and secondary alcohols can be used as substrates. Introduction of a N-heterocyclic carbene ligand to the catalyst considerably enhances the catalytic activity, and a very high turnover number of 950 has been obtained in the oxidation of 1-phenylethanol. The ­second is the N-alkylation of amines with alcohols. A new effective catalytic system consisting of [Cp*IrCl2]2/K2CO3 for the N-alkylation of primary amines with alcohols has been developed. Synthesis of indoles and 1,2,3,4-tetrahydroquinolines via intramolecular N-alkylation of amino alcohols and synthesis of nitrogen heterocycles via intermolecular N-alkylation of primary amines with diols catalyzed by a Cp*Ir complex have been also achieved. The third is the regio- and chemoselective transfer hydrogenation of quinolines. An efficient method for the transfer hydrogenation of quinolines catalyzed by [Cp*IrCl2]2/HClO4 using 2-propanol as a hydrogen source has been realized. A variety of 1,2,3,4-tetrahydroquinoline derivatives can be synthesized by this method. These results show that Cp*Ir complexes can be useful catalysts for hydrogen transfer ­reactions from the viewpoint of developing environmentally benign organic synthesis.

  • 1 Introduction

  • 2 Hydrogen Transfer Oxidation of Primary and Secondary Alcohols (Oppenauer-Type Oxidation)

  • 3 N-Alkylation of Amines with Alcohols

  • 4 Synthesis of N-Heterocyclic Compounds

  • 4.1 Intramolecular N-Heterocyclization of Amino Alcohols

  • 4.2 Intermolecular N-Heterocyclization of Primary Amines with Diols

  • 5 Transfer Hydrogenation of Quinolines

  • 6 Conclusion

Key words

iridium - catalysis - hydrogen transfer - alcohols - amines