Synthetic Catalysts Based on Reversible Covalent Bond Formation

基于可逆共价键形成的合成催化剂

• 批准号: 8822683
• 负责人: Anthony Czarnik
• 金额: --
• 依托单位: Ohio State University Research Foundation -DO NOT USE
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-06-15 至 1992-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8822683&HistoricalAwards=false
• 关键词: Synthetic; Catalysts; Based; Reversible; Covalent

This project by Anthony Czarnik of Ohio State University is within the Organic Dynamics Program, and will investigate the rate of organic reactions based on proximity effects. Model chemical systems will be designed so that reactants and catalysts will be brought together by stable chemical bonds which may later be broken through known, reversible chemical reactions. This work will lead to increased knowledge about the way molecules recognize one another. Work will be continued on the development of catalytic systems based on reversible covalent bond formation that will mediate synthetic conversions of alpha,beta-unsaturated carbonyl compounds. In this context, work will continue on the Diels-Alder approach to enzyme models and enzyme mimics. Methods to remove the degree of freedom between ligand and functional groups in cycloadducts will be investigated using bridged imidazole-anthracenes and tetraazaanthracene adducts, as well as the adducts with 2,5-bis(TMEDA)furan. The reverse Michael addition reaction will also be explored as a basis for catalytic cycles operating at much lower temperatures than the cycloaddition processes. Metal complexes based on the "proton- sponge" structure (N,N,N'-trimethyl-1,8-diaminonaphthalene) will be evaluated as Michael donors and as part of activated Michael adducts. An analysis of the metal-catalyzed retro Michael reaction is also planned.

俄亥俄州州立大学的安东尼·查尼克的这个项目是 在有机动力学计划，并将调查 基于邻近效应的有机反应速率。 模型 化学系统将被设计成使得反应物和 催化剂将通过稳定的化学键结合在一起 这可能会在以后被已知的可逆化学物质所突破 反应. 这项工作将增加对以下方面的了解： 分子间相互识别的方式 将继续进行开发催化系统的工作 基于可逆共价键的形成， α，β-不饱和羰基的合成转化 化合物. 在这方面，将继续开展工作， 酶模型和酶模拟物的Diels-Alder方法。 方法去除配体与配体之间的自由度， 环加合物中的官能团将使用 桥连咪唑-蒽和四氮杂蒽加合物， 以及与2，5-双（TMEDA）呋喃的加合物。 反向 迈克尔加成反应也将被探索作为一个基础， 催化循环的运行温度远低于 环加成过程。 基于“质子- 海绵”结构（N，N，N '-三甲基-1，8-二氨基萘） 将被评估为迈克尔捐赠者，并作为激活的一部分 迈克尔加合物。 金属催化还原的分析 迈克尔反应也在计划中。