ChalBondCat

查尔邦德猫

• 批准号: EP/X02329X/1
• 负责人: Andrew Smith
• 金额: $ 26万
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FX02329X%2F1
• 关键词: ChalBondCat

Chiral tertiary amine Lewis bases are proficient catalysts for a range of enantioselective transformations, with isothioureas regarded as versatile catalysts within this field. The observed reactivity and selectivity in isothiourea-catalyzed processes is hypothesized to primarily derive from an intramolecular 1,5-O---S interaction within key reaction intermediates, identified through computation and solid-state crystallographic analysis. Recognition of this 1,5-O---S motif as a chalcogen bond offers significant opportunities for exploitation and development. Building on these ideas, this proposal will develop a range of catalytically effective isochalcogenourea Lewis bases alongside a quantitative underpinning knowledge of their fundamental physical properties (such as nucleophilicity, Lewis basicity, pKaH). They will be benchmarked for catalytic activity (via kinetic analysis) and enantioselectivity, with the aim to develop a series of catalysts that operate effectively at ppm concentrations. The developed catalysts will subsequently be applied in a dynamic enantioselective reaction process to allow catalytic control over the absolute configuration of P(V) stereogenicity.

手性高等胺刘易斯碱基是一系列对映选择性转换的熟练催化剂，在该磁场内被视为多功能催化剂。假设在异硫库催化过程中观察到的反应性和选择性主要源自密钥反应中间体内的分子内1,5-O--S相互作用，这些相互作用通过计算和固态晶体学分析鉴定出来。认识到这1,5-O --- S主题作为chalcogen键，为开发和发展提供了重要的机会。在这些思想的基础上，该提案将开发一系列有效的等级等菌源刘易斯基地，以及对其基本物理特性的定量基础知识（例如亲核性，刘易斯碱性，pkah）。它们将通过基准进行催化活性（通过动力学分析）和对映选择性，旨在开发一系列在PPM浓度下有效运行的催化剂。随后，开发的催化剂将应用于动态对映选择性反应过程中，以允许对P（V）立体原性的绝对构型进行催化控制。