Isocyanide-Promoted Buchner Reaction of Ruthenium Carbenes: A Useful Mechanistic Tool to Study Ene-Yne and Alkene Metathesis

化学系的化学催化计划支持史蒂文·T·迪弗教授和杰罗姆·B·凯斯特教授的研究。Diver教授和Keister教授是纽约州立大学布法罗大学化学系的教员。烯-炔歧化反应是一种金属催化的反应，它将两个分子聚集在一起，一个分子具有碳-碳双键，另一个分子具有碳-碳三键。这两个分子在催化剂的作用下连接在一起。该反应在有机合成和材料化学中有着广泛的应用。然而，烯-炔反应很难研究，选择性也很难预测。该项目的目标是更好地了解中间体的结构和催化循环。更好地了解活性中间体有助于预测选择性和设计更好的催化剂。通过参与该项目，对研究生和本科生进行有机、有机金属和无机化学方面的培训。在小学层面的额外外展努力培养了渴望的年轻人的科学意识，并经常让学生第一次接触到分子在我们世界中的多种角色。格鲁卡宾促进了有机合成。烯烃歧化和烯炔歧化被广泛应用于天然产物、医药试剂和有机材料的合成。然而，催化中间体的分解和交叉复分解反应的低选择性是限制这些强有力的反应的效率和范围的两个基本问题。在这个合作项目中，由Diver博士和Keister博士领导的一个研究小组正在开发Buchner反应来捕获活性中间体，从而研究这些反应的机理。关键问题集中在Ru-乙烯基卡宾的分解途径和反应活性上。取代的乙烯基卡宾的反应性以前没有被评估过，尽管这些中间体在烯-炔途径中很重要。歧化反应的猝灭仍然是一个问题，而可靠、快速地猝灭各种Ru催化剂是该项目的一个重要目标。固体支撑型异氰化物正在被开发并用于猝灭和去除Ru卡宾。Diver博士在纽约州立大学布法罗分校为非专业学生开设了一门分子科学课程，以提高大学生的综合科学素养。

The Chemical Catalysis Program of the Chemistry Division supports the research of Professors Steven T. Diver and Jerome B. Keister. Professor Diver and Professor Keister are faculty members in the Department of Chemistry at the University at Buffalo, the State University of New York. Ene-yne metathesis is a metal-catalyzed reaction that brings together two molecules, one with a carbon-carbon double bond and the other with a carbon-carbon triple bond. The two molecules are linked together by the action of the catalyst. The reaction is widely used in organic synthesis and materials chemistry. The ene-yne reaction, however, is difficult to study and the selectivity is hard to predict. The goal of this project is to better understand the structure of the intermediates and the catalytic cycle. A better understanding of reactive intermediates facilitates the prediction of selectivity and the design of better catalysts. Graduate students and undergraduates are trained in organic, organometallic, and inorganic chemistry through their participation in the project. Additional outreach efforts at the elementary school level develop scientific awareness in eager young minds, and often give students their first exposure to the many roles of molecules in our world.The Grubbs ruthenium carbenes have improved organic synthesis. Alkene metathesis and ene-yne metathesis are widely used in the synthesis of natural products, pharmaceuticals agents, and organic materials. However, decomposition of catalytic intermediates and low selectivity in cross metathesis are two fundamental problems that limit the efficiency and scope of these powerful reactions. In this collaborative project, a research team led by Drs. Diver and Keister are developing the Buchner reaction to trap reactive intermediates and thus study of mechanism of these reactions. Key questions center on the decomposition pathways and reactivity of ruthenium vinyl carbenes. The reactivity of substituted vinyl carbenes has not been evaluated previously, despite the importance of these intermediates in the ene-yne pathway. Quenching of metathesis reactions continues to be a problem and reliable, rapid methods for quenching a wide variety of ruthenium catalysts is an important goal of the project. Solid-supported isocyanides are being developed and used for the quenching and removal of ruthenium carbenes. Dr. Diver presents a molecular science course for non-majors at SUNY Buffalo that increases general scientific literacy of the University students.