Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts.
英文:
Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts.
A review. This review article summarizes our recent researches for mol. design of polyoxometalates (POMs) and their related compds. for environmentally-friendly functional group transformations. The divacant POM [ﾎｳ-SiW10O34(H2O)2]4- exhibits high catalytic performance for mono-oxygenation-type reactions including epoxidn. of olefins and allylic alcs., sulfoxidn., and hydroxylation of organosilanes with H2O2. We have successfully synthesized several POM-based mol. catalysts (metal-substituted POMs) with controlled active sites by the introduction of metal species into the divacant POM as a "structural motif". These mol. catalysts can efficiently activate H2O2 (vanadium-substituted POM for epoxidn.) 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 addn., we have developed POM-based "mol. heterogeneous catalysts" by the "solidification" and "immobilization" of catalytically active POMs. [on SciFinder(R)]
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