Synthesis of Coordinatively Unsaturated Iron Complexes and C-H Bond Activation

配位不饱和铁配合物的合成及C-H键活化

• 批准号: 20613004
• 负责人: OHKI Yasuhiro
• 金额: $ 2.83万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20613004/
• 关键词: 鉄; C-H結合活性化; 配位不飽和; 有機金属; 触媒; 有機金属錯体; N-ヘテロ環カルベン

The activation of C-H bonds is a key elementary step of organometallic reactions, and has great utility in organic synthesis. As a requirement for successful C-H bond activation under mild conditions would be preparation of coordinatively unsaturated complexes, we have synthesized coordinatively unsaturated half-sandwich iron complexes of N-heterocyclic carbenes. The sequential C-H bond activation and borylation reactions were found to occur upon treatment of the iron complexes with thiophene, furan, benzothiophene, benzofuran, or pyridine, followed by addition of hydroboranes. Based on these findings on stoichiometric reactions, we have developed the catalytic C-H bond activation/borylation of furans and thiophenes mediated by a half-sandwich iron complex of the methyl-substituted N-heterocyclic carbene. We have also conducted a series of reactions of the new iron complexes with nearly stoichiometric amount of substrate, to gain mechanistic insights.

碳氢键的活化是有机金属反应的关键步骤，在有机合成中具有重要的应用价值。由于在温和条件下成功激活C-H键的条件是制备配位不饱和配合物，我们合成了n -杂环碳烯的配位不饱和半夹心铁配合物。在用噻吩、呋喃、苯并噻吩、苯并呋喃或吡啶处理铁配合物后，再加入氢硼烷，依次发生C-H键活化和硼化反应。基于这些化学计量反应的发现，我们开发了甲基取代n杂环碳的半夹心铁配合物介导的呋喃和噻吩的C-H键活化/硼化反应。我们还进行了一系列新的铁配合物与接近化学计量量的底物的反应，以获得机理的见解。

项目成果

現代化学増刊44 有機金属化学最前線:多様な元素をつかいこなす

现代化学特刊第44期：有机金属化学前沿：多种元素的利用

• 发表时间: 2011
• 作者: Tetsumi Tanabe;Koji Noda;Satoshi Miyagi;Noriyuki Kurita;Shigenori Tanaka;Julia Setzler;Wolfgang Wenzel;Evgeni B. Starikov;Gianaurelio Cuniberti;大木靖弘
• 通讯作者: 大木靖弘

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2, 6-(mesityl)2} and reversible CO addition at the Ni site

• DOI: 10.1073/pnas.0913399107
• 发表时间: 2010-03-02
• 期刊: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• 影响因子: 11.1
• 作者: Ohki, Yasuhiro;Yasumura, Kazunari;Tatsumi, Kazuyuki
• 通讯作者: Tatsumi, Kazuyuki

Reactions at the Ru-S Bonds of Coordinatively Unsaturated Ruthenium Complexes Having Tethered 2,6-Dimesitylphenyl Thiolate

束缚 2,6-二苯基硫醇盐的配位不饱和钌配合物的 Ru-S 键反应

• 发表时间: 2008
• 期刊: Chem.Asian J. 3
• 作者: Yasuhiro Ohki;Yuko Takikawa;Hitomi Sadohara;Christian Kesenheimer;Barthel Engendahl;Elissavet Kapatsina;Kazuyuki Tatsumi
• 通讯作者: Kazuyuki Tatsumi

ニトロゲナーゼ活性部位の人工構築を目指して

旨在人工构建固氮酶活性位点

• 发表时间: 2009
• 作者: Yamago;S.; Kayahara;E.; Yamada;H.;南雲広樹・秋根茂久・鍋島達弥;大木靖弘;N. Miyaura;大木靖弘
• 通讯作者: 大木靖弘

ニトロゲナーゼおよび[NiFe]ヒドロゲナーゼ活性部位の人工構築

固氮酶和[NiFe]氢化酶活性位点的人工构建

• 发表时间: 2009
• 期刊: 触媒 63
• 作者: 大木靖弘;巽和行
• 通讯作者: 巽和行