Development of Selective Oxidation Catalyst by Control of Multi-Nuclear Active Site of Transition Metal and Reaction Field

控制过渡金属多核活性位点和反应场的选择性氧化催化剂的研制

• 批准号: 18065002
• 负责人: MIZUNO Noritaka
• 金额: $ 44.54万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2009
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-18065002/
• 关键词: 多核遷移金属活性点; 反応場; 選択酸化; 触媒; 多核金属活性点; ポリオキソメタレート; 銅; 多核活性点; アルキン; 酸化的ホモカップリング; オレフィン; エポキシド; エポキシ化反応; バナジウム; 過酸化水素; 固定化触媒

We have developed the efficient oxidation catalysts such as the divacant lacunary polyoxotungstates and divanadium-substituted polyoxotungstate. The multi-nuclear active sites can activate H_2O_2 and substrates efficiently, resulting in the high catalytic performance for the epoxidation of olefins and Bayer-Villiger oxidation with H_2O_2. The novel selenium-containing dinuclear tungsten species shows the highest catalytic activity for H_2O_2-based epoxidation of homoallylic and allylic alcohols among selenium and tungsten complexes. The stabilization of the transition-state by the hydrogen bonding results in the high reactivity. We have also developed the dicopper-substituted γ-Keggin silicotungstate that can act as an effective homogeneous catalyst for the oxidative homocoupling of alkynes and regioselective 1,3-dipolar cycloaddition of organic azides to alkynes. The cooperative involvement of two copper centers in catalyzing the present reactions has been proposed.

我们开发了双空位多钨酸盐和双钒取代多钨酸盐等高效氧化催化剂。多核活性中心能有效地活化H_2O_2和底物，从而对烯烃环氧化反应和H_2O_2的Bayer-Villiger氧化反应具有良好的催化性能。在硒钨配合物中，新型含硒双核钨催化剂对高烯丙醇和烯丙醇的H_2O_2环氧化反应具有最高的催化活性。通过氢键稳定过渡态导致高反应性。我们还开发了双铜取代的γ-Keggin硅钨酸盐，它可以作为一种有效的均相催化剂，用于炔的氧化偶联和有机叠氮化物与炔的区域选择性1，3-偶极环加成反应。提出了两个铜中心在催化本反应中的协同参与。

项目成果

Selective aerobic oxidations by supported ruthenium hydroxide catalysts

• DOI: 10.1016/j.cattod.2007.12.026
• 发表时间: 2008-03-31
• 期刊: CATALYSIS TODAY
• 影响因子: 5.3
• 作者: Mizuno, Noritaka;Yamaguchi, Kazuya
• 通讯作者: Yamaguchi, Kazuya

Efficient catalytic synthesis of tertiary and secondary amines from alcohols and urea.

• DOI: 10.1002/anie.200905385
• 发表时间: 2009-12
• 期刊: Angewandte Chemie
• 作者: Jinling He;J. Kim;K. Yamaguchi;N. Mizuno

Liquid Phase Oxidation Catalyzed by Polyoxometalates (Surface and Nanomolecular Catalysis(分担執筆))

多金属氧酸盐催化的液相氧化（表面和纳米分子催化（贡献者））

• 发表时间: 2006
• 作者: N.Mizuno;K.Kamata;K.Yamaguchi
• 通讯作者: K.Yamaguchi

Selective Oxidation Catalyzed by Polyoxometalate

多金属氧酸盐催化的选择性氧化

• 发表时间: 2007

An Immobilized Organocatalyst for Cyanosilylation and Epoxidation.

用于氰甲硅烷基化和环氧化的固定化有机催化剂。

• DOI: 10.1002/chin.200650100
• 发表时间: 2006
• 期刊: ChemInform
• 作者: K. Yamaguchi;Toru Imago;Y. Ogasawara;J. Kasai;M. Kotani;N. Mizuno
• 通讯作者: N. Mizuno