Development of effecient and stereoselective Non-heme type catalyst by introduction of stereocontrol

通过引入立体调控开发高效立体选择性非血红素型催化剂

• 批准号: 14540519
• 负责人: MIYAKE Hiroyuki
• 金额: $ 2.18万
• 依托单位: Osaka City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540519/
• 关键词: Optical Active; Dinuclear Complex; Oxidation Reaction; Catalyst; Hydrogen Peroxide; Non-heme Type; Sulfide; Stereo Control

Stereoselective oxidation is an important chemical process in academy and / or industry and iron complexes with high efficiency and high stereoselectivity are required for environmentally friendly process. Since a dinuclear core structure of iron(III) complex developed by us is a key core structure of nonheme dinuclear iron enzyme such as alkane monooxygenase, it has been studied enhancing the catalytic oxidation properties of the synthesized dinuclear iron(III) complexes by means of introduction of chiral substitute and I or sterically hindered substitutes in the ligands. Several N2O2 chiral tetradentate ligand including amide binding sites external to the ethylenediamine and their dinuclear iron(III) complexes have been synthesized. The catalytic properties for sulfoxidation with hydrogen peroxidewere examined. The iron(III) complex with chiral ligand including tertiary amides is most active compared to the complexes including secondary amide nor achiral ligands. To study the structural detail of these complexes, mononuclear metal complexes with these chiral ligands have been examined and it was clear that the structure of metal complex with chiral ligand including secondary amine is opposite to that if metal complex with chiral ligand including tertiary amides. The helicity of the complex is also influenced by counter anions.

立体选择性氧化是一个重要的化工过程，环境友好的过程需要高效率和高立体选择性的铁配合物。由于我们开发的双核铁（III）配合物的核心结构是非血红素双核铁酶（如烷烃单加氧酶）的关键核心结构，因此研究了通过在配体中引入手性取代基和I或空间位阻取代基来增强所合成的双核铁（III）配合物的催化氧化性能。合成了几种含酰胺键的N_2O_2手性四齿配体及其双核铁配合物。考察了该催化剂对过氧化氢磺基氧化反应的催化性能。与包括仲酰胺或非手性配体的配合物相比，具有包括叔酰胺的手性配体的铁（III）配合物是最具活性的。为了研究这些配合物的结构细节，已经检查了具有这些手性配体的单核金属配合物，并且清楚的是，具有包括仲胺的手性配体的金属配合物的结构与具有包括叔酰胺的手性配体的金属配合物的结构相反。配合物的螺旋度也受到抗衡阴离子的影响。

项目成果

H.Miyake, K.Yoshida, H.Sugimoto, H.Tsukube: "Dynamic Helicity Inversion by Achiral anion Stimulus in synthetic Cobalt(II) complexes System"J.Am.Chem.Soc.. 126. 6524 (2004)

H.Miyake、K.Yoshida、H.Sugimoto、H.Tsukube：“合成钴 (II) 配合物系统中非手性阴离子刺激的动态螺旋性反转”J.Am.Chem.Soc.. 126. 6524 (2004)

H.Miyake, K.Yoshida, H.Sugimoto, H.Tsukube: "Dynamic Helicity Inversion by Achiral Anion Stimulus in Synthetic Cobalt(II) Complexes System."J.Am.Chem.Soc.. 126. 6524-6525 (2004)

H.Miyake、K.Yoshida、H.Sugimoto、H.Tsukube：“合成钴 (II) 配合物系统中非手性阴离子刺激的动态螺旋性反转。”J.Am.Chem.Soc.. 126. 6524-6525 (2004)

三宅弘之, 築部 浩: "金属錯体を活用する分子プログラミング-らせん構造の構築と反転スイッチング"化学. 59. 70-71 (2004)

Hiroyuki Miyake、Hiroshi Tsukibe：“使用金属配合物的分子编程 - 螺旋结构的构建和反转转换”化学 59. 70-71 (2004)。

H.Miyake, H.Tsukube: "Molecular Programming by Metal Complexes"Kgaku. 59. 70 (2004)

H.Miyake、H.Tsukube：“金属配合物的分子编程”Kgaku。