ChalBondCat

手性叔胺刘易斯碱是一系列对映选择性转化的熟练催化剂，异硫脲被认为是该领域的多功能催化剂。在异硫脲催化过程中观察到的反应活性和选择性假设主要来源于关键反应中间体的分子内1,5- o -S相互作用，通过计算和固态晶体学分析确定。认识到这个1,5- o -S基序是一个硫键，为开发和开发提供了重要的机会。在这些想法的基础上，本提案将开发一系列催化有效的等硫原脲刘易斯碱基，以及对其基本物理性质（如亲核性、刘易斯碱度、pKaH）的定量基础知识。它们将被作为催化活性（通过动力学分析）和对映体选择性的基准，目的是开发一系列在ppm浓度下有效运行的催化剂。开发的催化剂随后将应用于动态对映选择反应过程，以允许对P(V)立体性的绝对构型进行催化控制。

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.