Shape-selective Oxidation Catalyzed by Sterically Controlled Metalloporphyrins

空间控制金属卟啉催化的择形氧化

• 批准号: 61470041
• 负责人: MIYAMOTO Takeshi
• 金额: $ 3.2万
• 依托单位: The university of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470041/
• 关键词: Synthetic Porphyrins; Hypochlorite; Epoxidation; Enzymatic Process; Porphyrin Catalyst; 触媒耐久性; ポルフィリン; 次亜塩素酸; 酵素類似機能

New types of synthetic metalloporphyrin catalyzed epoxidation of olefins. The reaction was carried out in dichloromethane-water system by use of hypochlorite as an oxygen source. In the oxygenation of styrene catalyzed by an atropisomeric manganese porphyrin(<alpha><alpha> <alpha><alpha> isomer), the reaction took place in the preference for open site to the crowded one. Several orthosubstituted tetraphenylporphyrins were prepared:The ortho positions were substituted by nitro, fluoro or chloro groups. Their complexes showed high stability to the decomposition of catalyst. By use of these iron(III) complexes, we developed the iron porphyrin-hypochlorite system to efficient catalyst. The initial rate of the epoxidation exhibited the substrate saturation kinetics similar to the enzymatic process. From the systematic survey of epoxidation catalyzed by these metalloporphyrins, it is evident that Michaelis-Menten's parameters and and product selectivity are influenced by shape of catalysts. In addition it was indicated that the epoxidation mechanism is different between manganese and iron catalysts.

新型合成金属卟啉催化烯烃环氧化。反应在二氯甲烷-水体系中以次氯酸盐为氧源进行。在阻转异构体锰卟啉（<α><α><α><α异构体）催化的苯乙烯氧化反应中，反应优先发生在开放位点而非拥挤位点。制备了几种邻位取代的四苯基卟啉：邻位被硝基、氟或氯基团取代。它们的配合物对催化剂的分解表现出较高的稳定性。通过使用这些铁(I​​II)配合物，我们开发了铁卟啉-次氯酸盐体系作为高效催化剂。环氧化的初始速率表现出与酶促过程类似的底物饱和动力学。从这些金属卟啉催化的环氧化反应的系统研究可以看出，米氏参数和产物选择性受催化剂形状的影响。此外，表明锰催化剂和铁催化剂的环氧化机理不同。

项目成果

S. Takagi;T. K. Miyamoto;Y. Sasaki: Bull. Chem. Soc. Jpn.59. 2371-2373 (1986)

S.高木；T.

高木繁,宮本健,佐佐木行美: Bull.Chem.Soc.Jpn.59. 2371-2373 (1986)

高木茂、宫本健、佐佐木幸美：Bull.Chem.Soc.Jpn.59 (1986)。

高橋英太郎, 天津裕之, 宮本健, 佐佐木行美: 日本化学会誌. (1988)

Eitaro Takahashi、Hiroyuki Amatsu、Ken Miyamoto、Yukimi Sasaki：日本化学学会杂志（1988 年）。

E,Takahashi, H,Amatsu, T. K.Miyamoto,Y,Sasaki: "Development of the Porphyrin Complexes as the Robust.Homogeneous Catalyst and the Catalytic Epoxidation Reactions Similar to the Enzymatic Process of Crtochrome P450 --Fe(III) and Mn(III) Complexes of 5,10,1

E,Takahashi, H,Amatsu, T. K.Miyamoto,Y,Sasaki：“作为稳健均质催化剂的卟啉配合物的开发以及类似于 Crtochrome P450 --Fe(III) 和 Mn(III) 酶促过程的催化环氧化反应

S. Takagi;T. K. Miyamoto;Y. Sasaki ed. by: An Upique Atropisomeric Porphyrin Sysyem for Catalytic Oxygenation in The Role of Oxygen in Chemistry and Biochemistry. (1988)

S.高木；T.