Exceptional Selectivities of Dirhodium Catalysts

在这个由化学部化学催化项目资助的项目中，Michael P. Doyle教授将探索在催化有机合成和理解其应用方面具有变革潜力的dirhodium化合物。研究将集中在三个主要举措上。(1)羧酸二钠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过氧化氢氧化的机制，以及设计过氧化/迈克尔加成/过氧化裂解的合成策略。(2)开发了在Lewis酸催化反应中具有高对映选择性的酸性手性（II，III）羧甲酸二钠，并扩大了其在Lewis酸催化反应（包括羰基烯、亨利和亚甲基环加成反应）中的广泛应用。(3)发展对催化的理解和控制，即使用不同的催化剂（例如，通过金属碳烯或酸中间体），从相同的反应物产生不同的产物。目标是在乙烯基重氮乙酸酯的反应中建立催化剂的独特性，并设计有用的预测如何开发新的反应。这项研究提供了催化的基本进展，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。学生被整合到研究项目中，并有一个强大的指导项目，为他们的预期职业生涯做好准备。作为学生教育的一个平台，新的钯催化剂的开发及其在高选择性工艺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。由镝化合物催化的新氧化方法促进了绿色化学的选择性和高效应用，了解它们是如何发生的增加了分子氧作为氧化剂使用的潜力。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路易斯酸，用作碳-碳键形成转化的催化剂。在催化反应中寻找不同的结果是一个概念，其应用对一般的催化剂比较具有实际意义；使用两种或两种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.