caa a22 4500 445870613 CHVBK 20180317145510.0 cr unu---uuuuu 170323e20110601xx s 000 0 eng 10.1007/s10563-011-9111-2 doi (NATIONALLICENCE)springer-10.1007/s10563-011-9111-2 Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts [Elektronische Daten] [Noritaka Mizuno, Kazuya Yamaguchi, Keigo Kamata] 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. Springer Science+Business Media, LLC, 2011 Polyoxometalate nationallicence Molecular design nationallicence Controlled active sites nationallicence Molecular heterogeneous catalysts nationallicence Environmentally-friendly functional group transformations nationallicence Mizuno Noritaka Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, 113-8656, Bunkyo-ku, Tokyo, Japan aut Yamaguchi Kazuya Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, 113-8656, Bunkyo-ku, Tokyo, Japan aut Kamata Keigo Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, 113-8656, Bunkyo-ku, Tokyo, Japan aut Catalysis Surveys from Asia Springer US; http://www.springer-ny.com 15/2(2011-06-01), 68-79 1571-1013 15:2<68 2011 15 10563 https://doi.org/10.1007/s10563-011-9111-2 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10563-011-9111-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Mizuno Noritaka Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, 113-8656, Bunkyo-ku, Tokyo, Japan aut NATIONALLICENCE 700 1- Yamaguchi Kazuya Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, 113-8656, Bunkyo-ku, Tokyo, Japan aut NATIONALLICENCE 700 1- Kamata Keigo Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, 113-8656, Bunkyo-ku, Tokyo, Japan aut NATIONALLICENCE 773 0- Catalysis Surveys from Asia Springer US; http://www.springer-ny.com 15/2(2011-06-01), 68-79 1571-1013 15:2<68 2011 15 10563 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer