Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts |
| |
Authors: | Noritaka Mizuno Kazuya Yamaguchi Keigo Kamata |
| |
Affiliation: | (1) Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku Tokyo, 113-8656, Japan |
| |
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. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|