Hydrogen Bonds as Control Elements to Direct the Selectivity of Transition Metal-Catalyzed Reactions

氢键作为控制元素来指导过渡金属催化反应的选择性

• 批准号: 212748935
• 负责人: Professor Dr. Thorsten Bach
• 金额: --
• 依托单位: Lehrstuhl für Organische Chemie I
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/212748935?language=en
• 关键词: Hydrogen; Bonds; Control; Elements; Direct

The project aims at the development of catalysts, which allow for a simultaneous control of the molecular position, at which a chemical reaction takes place, and of the absolute configuration of the stereogenic center, which is formed during the reaction. Hydrogen bonds are employed to pre-coordinate a substrate to the chiral ligand of a transition metal. As a result the spatial proximity of the catalytically active center determines the regioselectivity of the transformation while the enantioselectivity is determined by the non-covalent interaction. Six key reactions are to be studied in which oxenoid, nitrenoid or carbenoid species attack either a double bond or a C-H bond. Ideal distances between the individual substrates and the transition metal center are to be optimized. Studies to possible application of the methods in natural product synthesis supplement the Project.

该项目旨在开发催化剂，允许同时控制化学反应发生的分子位置和反应过程中形成的立体中心的绝对构型。氢键用于将底物预配位到过渡金属的手性配体。因此，催化活性中心的空间接近性决定了转化的区域选择性，而对映选择性由非共价相互作用决定。六个关键的反应是要研究的oxenoid，nitrenoid或carbenoid物种攻击双键或C-H键。要优化各个衬底与过渡金属中心之间的理想距离。本项目对天然产物合成方法的可能应用进行了研究。

项目成果

Synergistic Stereocontrol in the Enantioselective Ruthenium-Catalyzed Sulfoxidation of Spirodithiolane-Indolones.

螺二硫戊环-吲哚酮对映选择性钌催化磺化氧化中的协同立体调控

• DOI: 10.1002/chem.201501780
• 发表时间: 2015
• 期刊: Chemistry
• 作者: F. Zhong;A. Pöthig;T. Bach
• 通讯作者: T. Bach

Enantioselective construction of 2,3-dihydrofuro[2,3-b]quinolines through supramolecular hydrogen bonding interactions.

• DOI: 10.1002/chem.201404617
• 发表时间: 2014-10
• 期刊: Chemistry
• 作者: F. Zhong;T. Bach