Iminium Ion Catalysis: Chemical and theoretical tools to understand the catalytic cycle

亚胺离子催化：了解催化循环的化学和理论工具

• 批准号: EP/E018718/1
• 负责人: James Platts
• 金额: $ 32.7万
• 依托单位: CARDIFF UNIVERSITY
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE018718%2F1
• 关键词: Iminium; Ion; Catalysis; Chemical; theoretical

Metal free processes are increasingly used to develop novel, cleaner, more efficient and selective transformations in synthetic chemistry. Much recent interest has centred on iminium ion and enamine catalysis using cyclic secondary amines, which has been shown to be an effective platform a wide range of reactions, providing a wealth of new methods with which to perform standard synthetic protocols in high yield and enantiomeric excess. Despite impressive advances in recent years, however, a detailed understanding of the mechanisms for these reactions remains elusive and catalyst design remains essentially a hit-and-miss affair.We propose to address this fundamental lack of knowledge by carrying out a series of physical measurements of key quantities, such as rate constants and activation barriers, for individual steps involved in iminium ion catalysis, and ultimately to the entire catalytic cycle. Such measurements will be complemented by theoretical calculations of reaction mechanisms, already underway in our group. In this way, we will augment the existing high profile synthetic methodologies using this practically simple and mechanistically fascinating class of transformation, and ultimately facilitate rational design of new, more efficient catalysts.

无金属工艺越来越多地用于开发合成化学中的新型、更清洁、更有效和更选择性的转化。最近的兴趣集中在亚胺离子和烯胺催化使用环状仲胺，这已被证明是一个有效的平台，广泛的反应，提供了丰富的新方法，其中执行标准的合成方案，在高产率和对映体过量。尽管近年来取得了令人印象深刻的进展，然而，这些反应的机制的详细了解仍然难以捉摸，催化剂的设计仍然基本上是一个击中和错过的事情。我们建议通过进行一系列的物理测量的关键量，如速率常数和活化势垒，在亚胺离子催化的各个步骤，并最终影响整个催化循环。这些测量将通过我们小组已经进行的反应机制的理论计算来补充。通过这种方式，我们将使用这种实际上简单且机械上迷人的转化类来增强现有的高调合成方法，并最终促进新的更有效的催化剂的合理设计。

项目成果

Lewis base catalysis 2: Primary and secondary amines for iminium ion catalysis

路易斯碱催化2：用于亚胺离子催化的伯胺和仲胺

• 发表时间: 2009
• 作者: Brazier

Iminium Ion Catalysis: Tools and Observations

亚胺离子催化：工具和观察

• 发表时间: 2009
• 作者: N/a Brazier

On the Roles of Protic Solvents in Imidazolidinone-Catalyzed Transformations

质子溶剂在咪唑啉酮催化转化中的作用

• DOI: 10.1002/ange.201005892
• 发表时间: 2011
• 期刊: Angewandte Chemie
• 作者: Brazier J

On the roles of protic solvents in imidazolidinone-catalyzed transformations.

关于质子溶剂在咪唑啉酮催化转化中的作用。

• DOI: 10.1002/anie.201005892
• 发表时间: 2011
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Brazier JB