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

异氰化物促进的钌卡宾布赫纳反应：研究烯炔和烯烃复分解的有用机械工具

• 批准号: 1566162
• 负责人: Steven Diver
• 金额: $ 48万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1566162&HistoricalAwards=false
• 关键词: Isocyanide; Promoted; Buchner; Reaction; Ruthenium

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.

化学系的化学催化计划支持教授史蒂芬T。戴弗和杰罗姆B。凯斯特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-炔复分解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。 更好地理解活性中间体有助于预测选择性和设计更好的催化剂。 研究生和本科生通过参与该项目接受有机，有机金属和无机化学方面的培训。 在小学阶段的额外推广工作在渴望的年轻头脑中培养科学意识，并经常让学生第一次接触到我们世界中分子的许多作用。格拉布斯钌卡宾改进了有机合成。烯烃复分解反应和烯-炔复分解反应广泛应用于天然产物、药物和有机材料的合成。然而，催化中间体的分解和交叉复分解中的低选择性是限制这些强大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。关键问题集中在钌乙烯基卡宾的分解途径和反应性上。取代的乙烯基卡宾的反应性以前没有被评估，尽管这些中间体在烯-炔途径中的重要性。复分解反应的淬灭仍然是一个问题，并且用于淬灭各种钌催化剂的可靠、快速方法是该项目的重要目标。固体负载的异腈正被开发并用于淬灭和除去钌卡宾。戴弗博士为纽约州立大学布法罗的非专业学生提供了一门分子科学课程，以提高大学生的一般科学素养。