Exceptional Selectivities of Dirhodium Catalysts

在这个由化学系化学催化计划资助的项目中，迈克尔·P·道尔教授将探索具有转化潜力的镝化合物，以促进有机合成催化的进步，并了解它们的应用。这项研究将集中在三个主要举措上。(1)碳酰胺二氢呋喃催化氧化有机化合物的研究进展。这些研究将包括阐明和澄清叔丁基氢过氧化氢的氧化机理，以及设计一种过氧化/Michael加成/过氧化氢裂解的合成策略。(2)在Lewis酸催化反应中开发高对映体选择性的酸性手性二氢呋喃(II，III)羧胺盐，并拓展其在Lewis酸催化反应(包括羰基-烯、Henry和甲亚胺环加成反应)中的广泛应用。(3)发展对催化的理解和控制，即通过使用不同的催化剂(例如，通过金属卡宾和酸性中间体)，从相同的反应物中唯一地产生不同的产物。目标是建立重氮乙酸乙烯酯反应中催化剂的独特性，并设计关于如何开发新反应的有用预测。这项研究提供了催化方面的基本进展，并为准备从事化学科学职业的研究生和本科生的教育提供了研究机会。学生通过强大的指导计划融入研究计划，为他们预期的职业生涯做好准备。作为学生教育的平台，高选择性过程中新的镝催化剂及其应用的开发提供了新的转化、增强的催化剂控制和特定的反应路径。由镝化合物催化的新的氧化方法促进了选择性和高效的绿色化学应用，了解它们是如何发生的增加了使用分子氧作为氧化剂的潜力。通过温和的方法制备的氧化镝化合物提供了广泛的有效和高选择性的Lewis酸作为催化剂，用于碳-碳键的形成转化。在催化反应中寻找不同的结果是一个概念，其应用对催化剂的总体比较具有实际意义；使用两个或两个以上相互独立的催化剂将提高许多催化过程的效率。

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Michael P. Doyle will explore dirhodium compounds that hold transformational potential for advancements in catalysis for organic synthesis and for the understanding of their applications. The research will focus on three major initiatives. (1) The development of catalytic oxidations of organic compounds using dirhodium carboxamidate. These studies will include the elucidation and clarification of the mechanisms of oxidations by tert-butyl hydroperoxide and the design of a synthetic strategy for peroxidation/Michael addition/peroxide cleavage. (2) The development of acidic chiral dirhodium(II,III) carboxamidates for high enantioselectivity in Lewis acid catalyzed reactions, and expanding their broad use in Lewis acid catalyzed reactions (including carbonyl-ene, Henry, and azomethine cycloaddition reactions). (3) The development of an understanding of and control of catalysis that exclusively produces different products from the same reactants by the use of different catalysts (e.g., through metal carbene versus acid intermediates). A goal is to establish catalyst uniqueness in reactions of vinyldiazoacetates and to design useful predictions about how to develop new reactions..This research provides fundamental advances in catalysis and offers research opportunities for the education of graduate and undergraduate students who are preparing for careers in the chemical sciences. Students are integrated into the research program with a strong mentoring program that prepares them for their intended careers. As a platform for student education, the development of new dirhodium catalysts and their applications for highly selective processes provides new transformations, enhanced catalyst control, and specific reaction pathways. New oxidation methodologies catalyzed by dirhodium compounds promote green chemistry applications that are selective and efficient, and understanding how they occur increases the potential for uses of molecular oxygen as the oxidant. Oxidized dirhodium compounds that are prepared by mild methods provide a broad selection of effective and highly selective Lewis acids for use as catalysts in carbon-carbon bond forming transformations. The search for divergent outcomes in catalytic reactions is a concept whose applications have practical implications for catalyst comparisons in general; the uses of two or more catalysts that act independent of each other will increase the efficiency of many catalytic processes.