Development of a Highly Efficient Complex Catalysts for Selective Aerobic Oxidation

用于选择性有氧氧化的高效复合催化剂的开发

• 批准号: 13640543
• 负责人: YAMADA Tohru
• 金额: $ 2.56万
• 依托单位: Keio University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640543/
• 关键词: Nitrous Oxide; Molecular Oxygen; Oxidation; Ruthenium Complex; Epoxidation; Aromatization; Porphyrin; Ouinone; 分子上酸素

In the presence of a catalytic amount of dioxo (tetramesitylporphyrinato) ruthenium (VI) complex, nitrous oxide (N_2O) oxidized trisubstituted olefins into the corresponding epoxides in good-to-high yields with high selectivity. Catalytic N_2O oxidation was successfully applied to various secondary and benzylic alcohols to afford the corresponding ketones and aldehydes in high yields. During the nitrous oxide oxidation of 9, 10-dihydroanthracene derivatives catalyzed by the ruthenium-porphyrin complexes, anthraquinones were selectively afforded by the C-H oxidation of the benzylic carbon under the appropriate reaction conditions, whereas anthracenes as a result of oxidative aromatization were selectively obtained in the presence of sulfuric acid. Preparation of 3-oxobutylideneaminato-rutheniumu complexes were also examined.A DFT study of the 3-oxobutylideneaminatocobalt (II) complex catalyzed cyclopropanation was performed to reveal the overall reaction pathway and the effects of the axial ligands. The reaction of cobalt (II) complexes with diazoacetate were traced by time-resolved FT-IR spectroscopy. It is generally considered that metal-carbene carbon bonds in carbene complexes should be double-bonded, however, the theoretical and FT-IR analyses revealed that the cobalt-carbene carbon bond was characterized as a single bond. It is expected that these observations would provide a promising method for design of oxidation catalysts.

在催化剂存在下，氧化亚氮(N_2O)以较高的选择性将三取代烯烃氧化成相应的环氧化物。将催化N2O氧化反应成功地应用于各种仲醇和苄醇，高产率地得到了相应的酮和醛。在Ru-卟啉配合物催化氧化9，10-二氢蒽衍生物的氧化亚氮反应中，在合适的反应条件下，苯基碳的C-H氧化反应选择性地生成了蒽醌类化合物，而在硫酸存在下，氧化芳构化反应选择性地生成了蒽类化合物。本文还研究了3-氧基丁亚氨基-Rutheniumu配合物的制备，并用密度泛函理论研究了3-氧基丁亚氨基钴(II)催化环丙烷化反应的全过程以及轴向配体的影响。用时间分辨傅里叶变换红外光谱跟踪了钴(II)络合物与重氮乙酸酯的反应。一般认为，卡宾络合物中的金属-卡宾碳键应该是双键的，然而，理论分析和FT-IR分析表明，钴-卡宾碳键是单键。这些观察结果可望为氧化催化剂的设计提供一种有前途的方法。

项目成果

H.Tanaka, T.Ikeno, and T.Yamada: "Efficient Oxidative Aromatization of 9, 10-Dihydroanthracenes with Molecular Oxygen Catalyzed by Ruthenium Porphyrin Complex"Synlett. 576-578 (2003)

H.Tanaka、T.Ikeno 和 T.Yamada：“钌卟啉配合物催化的分子氧对 9, 10-二氢蒽的高效氧化芳构化”Synlett。

橋本 健太郎ほか: "Nitrous Oxide Oxidation of Secondary and Benzylic Alcohols Using Ruthenium"Chemistry Letters. 2001. 922-923 (2001)

Kentaro Hashimoto 等人：“使用钌的一氧化二氮氧化仲醇和苯甲醇”化学快报 2001. 922-923 (2001)

K.Hashimoto, Y.Kitaichi, H.Tanaka, T.Ikeno, and T.Yamada: "Nitrous Oxide Oxidation of Secondary and Benzylic Alcohols Using Ruthenium Complex Catalyst"Chem.Lett.. 922-923 (2001)

K.Hashimoto、Y.Kitaichi、H.Tanaka、T.Ikeno 和 T.Yamada：“使用钌络合物催化剂对仲醇和苯甲醇进行一氧化二氮氧化”Chem.Lett.. 922-923 (2001)

K.Hashimoto, H.Tanaka, T.Ikeno, and T.Yamada: "Selective Nitrous Oxide Oxidation for C-H Oxidation and Aromatization of 9, 10-Dihydroanthracene Derivatives"Chem.Lett.. 582-583 (2002)

K.Hashimoto、H.Tanaka、T.Ikeno 和 T.Yamada：“选择性一氧化二氮氧化用于 9, 10-二氢蒽衍生物的 C-H 氧化和芳构化”Chem.Lett.. 582-583 (2002)

田中 寛隆 ほか: "Efficient Oxidative Aromatization of 9, 10-Dihydroanthracenes with Molecular Oxygen Catalyzed by Ruthenium Porphyrin Complex"Synlett. Vol.2003,No.4. 576-578 (2003)

Hirotaka Tanaka 等人：“钌卟啉配合物催化的 9, 10-二氢蒽的高效氧化芳构化”Synlett，第 2003 卷，第 576-578 期。