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Synlett 2010(16): 2365-2382  
DOI: 10.1055/s-0030-1258565
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Green Functional Group Transformations by Supported Ruthenium Hydroxide Catalysts

Kazuya Yamaguchi, Noritaka Mizuno*
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
Fax: +81(3)58417220; e-Mail: tmizuno@mail.ecc.u-tokyo.ac.jp;
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Publikationsverlauf

Received 22 April 2010
Publikationsdatum:
10. September 2010 (online)

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Abstract

This account summarizes our recent research on green functional group transformations using easily prepared supported ruthenium hydroxide catalysts [Ru(OH)x/support, support = Al2O3, TiO2, or Fe3O4]. Various kinds of functional group transformations, e.g. the oxidation (oxidative dehydrogenation) of alcohols and amines, hydrogen-transfer reactions, such as racemization and reduction, and the hydration of nitriles, can be promoted by the concerted activation of the substrates (including alcohols, amines, and nitriles) by the Lewis acid and Brønsted base sites on the Ru(OH)x/support catalyst. In addition, we have successfully developed three novel catalytic transformations with the Ru(OH)x/support catalysts: (1) the oxygenation of primary amines to give amides, (2) the direct oxidative synthesis of nitriles from primary alcohols and ammonia, and (3) the N-alkylation of ammonia (or its surrogates) with alcohols to produce symmetrically substituted tertiary or secondary amines. The catalyses for these transformations are truly heterogeneous, and the catalysts retrieved after the transformations can be reused with retention of their high catalytic performance.

1 Introduction

2 Preparation and Characterization of Supported Ruthenium Hydroxide Catalysts

3 Oxidation of Alcohols and Amines

4 Hydration of Nitriles

5 Oxygenation of Primary Amines To Give Amides

6 Direct Oxidative Synthesis of Nitriles from Primary Alcohols and Ammonia

7 N-Alkylation of Ammonia with Alcohols To Give Tertiary or Secondary Amines

8 Conclusion

Key words

concerted activation - Lewis acids - Brønsted bases - heterogeneous catalysis - ruthenium hydroxide

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