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.
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1 Introduction
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2 Hydrogen Transfer Oxidation of Primary and Secondary Alcohols (Oppenauer-Type Oxidation)
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3 N-Alkylation of Amines with Alcohols
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4 Synthesis of N-Heterocyclic Compounds
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4.1 Intramolecular N-Heterocyclization of Amino Alcohols
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4.2 Intermolecular N-Heterocyclization of Primary Amines with Diols
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5 Transfer Hydrogenation of Quinolines
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6 Conclusion
Key words
iridium - catalysis - hydrogen transfer - alcohols - amines
