Catalytic Platforms Using Aromatic Ions and Other Charged Species

使用芳香族离子和其他带电物质的催化平台

• 批准号: 10451705
• 负责人: Tristan H Lambert
• 金额: $ 47.24万
• 依托单位: CORNELL UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/10451705
• 关键词: Acidity; Acids; Address; Anatomy; Anions; Area; Biomedical Research; Catalysis; Charge; Chemicals; Complex; Development; Investigation; Ions; Lead; Learning; Molecular; Organic Synthesis; Preparation; Research; Speed; Stimulus; Structure; base; catalyst; chemical synthesis; design; driving force; innovation; novel; outcome prediction; programs

Project Summary. Chemical catalysis has long been a potent force for advancing biomedical research by enabling the construction of biologically important molecules with ever-increasing speed, efficiency, and versatility. One of the most potent driving forces for progress in the area of catalysis has been the discovery of new catalytic platforms and concepts. The proposed research program is broadly focused on advancing the area of catalysis through the development of novel catalytic platforms that utilize stable but electrically charged species as a key part of their molecular anatomy. In particular, we have employed aromatic ions such as cyclopropenium ion and cyclopentadienyl anion for the design of several highly effective catalyst platforms. For example, we introduced cyclopropenimines as a new class of strong, neutral superbase, and we have developed a number of chiral cyclopropenimines that have proven to be highly effective for enantioselective BrØnsted base catalyzed transformations. Moving forward, the major challenge in this area is to develop catalysts that are capable of engaging substrates of increasingly lower acidity while still maintaining control over stereoselectivity. Our continuing efforts are thus aimed at developing fundamentally new BrØnsted base platforms that will address this challenge. A second major application of aromatic ions that we have introduced is the pentacarboxycyclopentadienes (PCCPs) as a new platform for enantioselective BrØnsted acid catalysis. These catalysts are strongly acidic and are simple to prepare and to diversify, which stands in contrast to many of the established chiral BrØnsted acid platforms. In this area, the forefront challenge lies in learning how to generate and control the selectivity of increasingly unstabilized carbocation intermediates. Solving this challenge will require catalysts that are strongly acidic, chiral, and trivial to prepare, criteria which are very well satisfied by the PCCP platform. These and other investigations into the use of ionic structures to catalysis will continue to serve as a stimulus for advancements in chemical synthesis.

项目摘要。化学催化长期以来一直是推进生物医学研究的强大力量 能够以不断提高的速度、效率和能力构建具有生物学意义的重要分子 多功能性。催化领域进步最有力的驱动力之一是发现 新的催化平台和概念。拟议的研究计划主要侧重于推进 通过开发利用稳定但带电的新型催化平台来拓展催化领域 物种作为其分子解剖学的关键部分。特别是，我们使用了芳香族离子，例如 环丙烯离子和环戊二烯基阴离子用于设计几种高效催化剂平台。 例如，我们引入了环丙烯亚胺作为一类新的强中性超碱，并且我们有 开发了许多手性环丙烯亚胺，这些手性环丙烯亚胺已被证明对于对映选择性非常有效 布朗斯台德碱催化转化。展望未来，该领域的主要挑战是发展 能够与酸度逐渐降低的底物结合同时仍保持控制的催化剂 超过立体选择性。因此，我们不断努力的目标是开发全新的布朗斯特基地 将解决这一挑战的平台。我们介绍的芳香族离子的第二个主要应用 是五羧基环戊二烯（PCCP）作为对映选择性布朗斯台德酸催化的新平台。 这些催化剂呈强酸性，易于制备和多样化，这与许多催化剂形成鲜明对比。 已建立的手性布朗斯台德酸平台。在这个领域，最前沿的挑战在于学习如何 产生并控制越来越不稳定的碳阳离子中间体的选择性。解决这个问题 挑战将需要强酸性、手性且易于制备的催化剂，这些标准非常好 对PCCP平台感到满意。这些和其他关于使用离子结构催化的研究将 继续刺激化学合成的进步。