Molecular design of selective oxidation catalyst with polyoxometalate
Molecular design of selective oxidation catalyst with polyoxometalate
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DOI：
10.1016/j.cattod.2006.05.002
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发表时间：
2006-09
期刊：
影响因子：
5.3
通讯作者：
N. Mizuno;S. Hikichi;K. Yamaguchi;S. Uchida;Y. Nakagawa;Kazuhiro Uehara;Keigo Kamata
中科院分区：
文献类型：
--
作者：
N. Mizuno;S. Hikichi;K. Yamaguchi;S. Uchida;Y. Nakagawa;Kazuhiro Uehara;Keigo Kamata
报道了三种聚氧乙烯酸盐[γ-SiW 10 O34（H2O）2]4−（1）、[γ-1，2-H2SiV 2 W10 O 40]4−（2）和[W2 O3（O2）4（H2O）2]2−（3）的高效H2 O2基氧化体系。化合物1可以催化包括丙烯和1-辛烯等未活化末端烯烃在内的多种烯烃的环氧化反应，环氧化物的选择性≥99%，H2 O2的利用率≥99%。值得注意的是，2显示出独特的立体特异性，区域选择性，和非对映选择性的环氧化顺/反烯烃，非共轭二烯，3-取代的环己烯，分别。用1 equiv. 3能有效地催化水溶液中的H2 O2生成相应的环氧醇，产率较高。此外，催化剂3可以在保持催化性能的情况下再循环。
Efficient H2O2-based oxidation systems with three kinds of polyoxometalates, [γ-SiW10O34(H2O)2]4−(1), [γ-1,2-H2SiV2W10O40]4−(2), and [W2O3(O2)4(H2O)2]2−(3) are reported. The compound 1 can catalyze epoxidation of various olefins including non-activated terminal olefins such as propylene and 1-octene with ≥99% selectivity to epoxide and ≥99% efficiency of H2O2utilization. It is notable that 2 shows unique stereospecificity, regioselectivity, and diastereoselectivity for the epoxidation of cis/trans olefins, non-conjugated dienes, and 3-substituted cyclohexenes, respectively. The epoxidation of various allylic alcohols with only 1equiv. H2O2in water can be efficiently catalyzed by 3 to give the corresponding epoxy alcohols in high yields. Further, the catalyst 3 can be recycled with the maintenance of the catalytic performance.