RUI: Enhancing Undergraduate Chemical Education Through Research: The Experimental and Theoretical Investigation of Unusual Carbenes

RUI：通过研究加强本科化学教育：不寻常卡宾的实验和理论研究

• 批准号: 0315510
• 负责人: Dasan Thamattoor
• 金额: $ 20万
• 依托单位: Colby College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-07-15 至 2007-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0315510&HistoricalAwards=false
• 关键词: RUI; Enhancing; Undergraduate; Chemical; Education

Carbene-like products obtained from nitrogen-containing precursors may in fact come from the excited state of the precursors themselves. In addition, many nitrogenous precursors can be hazardous to handle or may simply not be synthetically available to generate carbenes of interest - e.g., a convenient and widely applicable method of generating a-hydroxycarbenes is currently unavailable. This proposal describes an undergraduate-oriented research program designed to study unusual carbenes generated from various cyclopropanated aromatics instead of conventional sources such as diazo compounds and diazirines. These non-nitrogenous precursors provide a safe, viable, and alternative route to carbene generation. Specific projects include the investigation a-hydroxycarbenes and novel heterocyclopropylcarbenes (including oxiranyl- and aziridinyl carbenes) and the generation of a-ketocarbenes to address key mechanistic issues in Wolff rearrangement processes. Electron spin resonance spectroscopy, time-resolved laser flash photolysis, and advanced computational methods will be brought to bear on the investigations as well. With this Research at Undergraduate Institutions Award, the Organic and Macromolecular Chemistry Program supports the research of Professor Dasan M. Thamattoor, of the Department of Chemistry at Colby College. Professor Thamattoor and his students are exploring, via theory and wet chemistry, the preparation, structure, and reactivity of unusual electron-deficient species known as carbenes. These unusual species play central roles in a wide variety of chemical processes, and development of a detailed understanding of their structure and reaction chemistry will lead to the development of better predictive tools for the control of chemical reactivity. Whereas other routes to some of the targeted carbenes are known, Professor Thamattoor's studies address serious questions about the structure and reactivity of the carbenes generated via these other routes, and in addition offer promise for the generation of new, previously unavailable carbenes. Through a partnership with the Maine Research Internships for Teachers and Students (MERITS) program, Professor Thamattoor will enhance the educational experience provided by this research program by including high school teachers and students.

从含氮前体获得的类卡宾产物实际上可能来自前体本身的激发态。此外，许多含氮前体处理起来可能很危险，或者根本无法通过合成来生成感兴趣的卡宾——例如，目前还没有一种方便且广泛适用的生成α-羟基卡宾的方法。该提案描述了一项面向本科生的研究计划，旨在研究由各种环丙烷芳烃而不是重氮化合物和二氮丙啶等传统来源产生的不寻常卡宾。这些非氮前体为卡宾的生成提供了安全、可行的替代途径。具体项目包括研究α-羟基卡宾和新型杂环丙基卡宾（包括环氧乙烷基和氮丙啶基卡宾）以及生成α-酮卡宾以解决沃尔夫重排过程中的关键机制问题。电子自旋共振光谱、时间分辨激光闪光光解和先进的计算方法也将应用于研究。凭借本科院校研究奖，有机和高分子化学项目支持科尔比学院化学系 Dasan M. Thamattoor 教授的研究。 Thamattoor 教授和他的学生正在通过理论和湿化学探索被称为卡宾的不寻常的缺电子物质的制备、结构和反应性。这些不寻常的物种在各种化学过程中发挥着核心作用，对其结构和反应化学的详细了解将有助于开发更好的预测工具来控制化学反应性。尽管一些目标卡宾的其他路线是已知的，但塔马图尔教授的研究解决了有关通过这些其他路线生成的卡宾的结构和反应性的严重问题，此外还为产生新的、以前无法获得的卡宾提供了希望。通过与缅因州教师和学生研究实习 (MERITS) 计划的合作，塔马图尔教授将通过让高中教师和学生参与来增强该研究计划提供的教育体验。