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Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts

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Abstract

This review article summarizes our recent researches for molecular design of polyoxometalates (POMs) and their related compounds for environmentally-friendly functional group transformations. The divacant POM [γ-SiW10O34(H2O)2]4− exhibits high catalytic performance for mono-oxygenation-type reactions including epoxidation of olefins and allylic alcohols, sulfoxidation, and hydroxylation of organosilanes with H2O2. We have successfully synthesized several POM-based molecular catalysts (metal-substituted POMs) with controlled active sites by the introduction of metal species into the divacant POM as a “structural motif”. These molecular catalysts can efficiently activate H2O2 (vanadium-substituted POM for epoxidation) and alkynes (copper-substituted POM for click reaction and oxidative homocoupling of alkynes). The aluminum-substituted POM exhibits Lewis acidic catalysis for diastereoselective cyclization of (+)-citronellal to (−)-isopulegol. In addition, we have developed POM-based “molecular heterogeneous catalysts” by the “solidification” and “immobilization” of catalytically active POMs.

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Acknowledgment

This work was accomplished through tremendous efforts of co-workers in our laboratory listed in the references (12, 16-21, 31, 44, 58, 59, 62, and 63). This work was supported in part by the Core Research for Evolutional Science and Technology (CREST) program of the Japan Science and Technology Agency (JST), the Global COE Program (Chemistry Innovation through Cooperation of Science and Engineering), and Grants-in-Aid for Scientific Researches from Ministry of Education, Culture, Sports, Science and Technology.

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Authors and Affiliations

  1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

    Noritaka Mizuno, Kazuya Yamaguchi & Keigo Kamata

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  1. Noritaka Mizuno
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  2. Kazuya Yamaguchi
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  3. Keigo Kamata
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Correspondence to Noritaka Mizuno.

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Mizuno, N., Yamaguchi, K. & Kamata, K. Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts. Catal Surv Asia 15, 68–79 (2011). https://doi.org/10.1007/s10563-011-9111-2

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