Polyfunctional Lewis Acid/Betaine Catalysts as New Bioinspired Tool for Asymmetric Synthesis

多官能路易斯酸/甜菜碱催化剂作为不对称合成的新仿生工具

• 批准号: 310990893
• 负责人: Professor Dr. René Peters
• 金额: --
• 依托单位: Institut für Organische Chemie (IOC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/310990893?language=en
• 关键词: Polyfunctional; Lewis; Acid; Betaine; Catalysts

A novel concept of synergistic catalysis is investigated exploring theintramolecular cooperation between a Lewis acid and a betaine. Aquasi naked aryloxide within the betaine acts as a Brønsted base todeprotonate a pronucleophile. The thus generated aromatic alcoholwithin the catalyst shall then activate and spatially control anelectrophile via a H-bond. It also serves as a proton source to enableturnover. An azolium moiety within the betaine shall also act a H-bonddonor, but could also allow for electrostatic interactions. We haverecently presented this concept of polyfunctional cooperative catalysisin literature in a study to form the otherwise rare diastereomers in 1,4-additions of ketoesters to nitroolefins. In initial follow-up studies wefound that this concept is broadly applicable. On the other hand –based on the reaction type– there can be distinct mechanisticdifferences. In the present proposal the primary goals are (1) toestablish the concept of cooperative Lewis acid / betaine catalysis invarious attractive stereoselective transformations, (2) if possible todevelop stereodivergent asymmetric processes, and (3) in particularto learn more about the polyfunctional mode of action by mechanisticstudies. Next to the development of efficient synthetic methods and astraightforward access to value-added chiral synthetic building blocks,we would like to create –via a knowledge based approach– aprofound basis for predictability and applicability in similar catalyticprocesses.

研究了一种新型的协同催化概念，以探索刘易斯酸与甜菜碱之间的分子内协调。甜菜碱内的赤氧化芳族芳氧化物充当质子核寄生虫的Brønsted碱。这样产生的芳族醇Within催化剂应通过H键激活并在空间控制厌氧脂。它也充当质子来源。甜菜碱内的硫雄部分也应作用于H键，但也可以允许进行静电相互作用。在一项研究中，我们在一项研究中介绍了这种多功能合作催化素文献的概念，该研究形成了硝基芬蛋白的1,4个酮症中的原本罕见的非对映异构体。在最初的后续研究中，该概念广泛适用。另一方面，基于反应类型 - 可能存在明显的机械差异。在本提案中，主要目标是（1）参与合作的概念刘易斯酸 /甜菜碱催化始终有吸引力的立体选择性转换，（2）如果可能的情况下，如果可能的话，如果可能发展了立体变态的不对称过程，并且（3）在Praceularto中，通过机械制定的多函数动作模式来了解更多有关机械函数的动作模式。除了开发有效的合成方法和对增值性手性合成构建基块的Astraightforward访问之外，我们想创建基于知识的方法 - 基于知识的方法 - 在类似催化过程中的可预测性和适用性。