Exceptional Selectivities of Dirhodium Catalysts

在这个由化学系化学催化计划资助的项目中，Michael P. Doyle教授将探索具有转化潜力的dirhodium化合物，以促进有机合成催化的进步，并了解其应用。研究将集中在三大举措上。(1)氨甲酰二铑催化氧化有机物之研究进展。这些研究将包括叔丁基过氧化氢的氧化机制的阐明和澄清，以及过氧化/迈克尔加成/过氧化物裂解的合成策略的设计。 (2)开发了在刘易斯酸催化反应中具有高对映体选择性的酸性手性二铑（II，III）羧酰胺化物，拓展了其在刘易斯酸催化反应（包括羰基-烯、亨利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从相同的反应物中专门产生不同的产物（例如，通过金属卡宾与酸中间体）。目标是建立重氮乙酸乙烯酯反应中的催化剂独特性，并设计有关如何开发新反应的有用预测。这项研究提供了催化的根本性进展，并为正在为化学科学职业做准备的研究生和本科生的教育提供了研究机会。 学生融入研究计划，有一个强大的指导计划，为他们的职业生涯做好准备。作为学生教育的平台，新的二铑催化剂的开发及其在高选择性过程中的应用提供了新的转化、增强的催化剂控制和特定的反应途径。 由二铑化合物催化的新的氧化方法促进了选择性和有效的绿色化学应用，并且理解它们如何发生增加了使用分子氧作为氧化剂的潜力。 通过温和方法制备的氧化二铑化合物提供了广泛的有效且高选择性的刘易斯酸选择，可用作碳-碳键形成转化中的催化剂。 在催化反应中寻找不同的结果是一个概念，其应用对催化剂的比较具有实际意义;使用两种或更多种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.