NSF Career: Enamine-Metal Lewis Acid Bifunctional Catalysts for Asymmetric Organic Transformations

迈阿密大学牛津校区的王宏教授在化学系化学催化（CAT）项目的支持下，开发了将金属中心和有机催化中心结合在单个分子上的双功能催化剂，用于不对称有机转化的潜在应用。合成双功能胺金属路易斯酸催化剂，用于不对称碳-碳和碳杂原子成键反应，这些反应离不开两个催化中心的协同作用。直接醛醇缩合与酮和反电按需杂diels - alder反应将进行研究。催化剂的设计允许不同的胺碱与不同的金属相结合，这扩大了这些双功能催化系统的适用性范围，以广泛的有机反应。刘易斯酸-刘易斯碱双功能体系的发展具有挑战性，因为酸和碱容易自猝灭和失活。提出的研究有望通过明智的分子结构来解决这个问题，该分子结构具有足够的灵活性，使有机碱和金属路易斯酸接近，但具有足够的刚性和位阻，以防止它们结合。本研究将对不对称催化及精细化学品和药物的合成产生重要影响。研究结果将被整合到一门新的催化研究生课程中，并将实施一项拓展计划，为来自德州农工大学金斯维尔分校的少数族裔本科生及其教师以及该地区高中的高中教师提供暑期研究经验。

Professor Hong Wang of Miami University Oxford Campus is supported by the Chemical Catalysis (CAT) Program in the Division of Chemistry to develop bifunctional catalysts combining a metal center with an organocatalytic center on a single molecule for potential applications in asymmetric organic transformations. Bifunctional enamine-metal Lewis acid catalysts will be synthesized and used for asymmetric carbon-carbon and carbon-heteroatom bond forming reactions which cannot be achieved without the synergistic action of the two catalytic centers. Direct aldol condensations with ketones and inverse-electron-demand hetero-Diels-Alder reactions will be investigated. The catalyst design allows for the combination of different amine bases with different metals, which broadens the spectrum of applicability of these bifunctional catalytic systems to a wide range of organic reactions. The development of Lewis acid-Lewis base bifunctional systems is challenging because the acid and the base are prone to self-quenching and inactivation. The proposed research promises to circumvent this problem by judicious molecular architecture with sufficient flexibility to bring the organic base and the metal Lewis acid into close proximity but with enough rigidity and steric hindrance to prevent their binding. The proposed research could significantly impact asymmetric catalysis and the synthesis of fine chemicals and pharmaceuticals. The results will be integrated into a new graduate course in catalysis and an outreach plan will be implemented to provide summer research experience to minority undergraduate students and their teachers from Texas A&M University-Kingsville and to high school teachers from area high schools.