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

从含氮前体得到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，或者根本无法合成产生感兴趣的碳烯-例如，目前还没有一种方便且广泛适用的生成a-羟基碳烯的方法。该提案描述了一个面向本科生的研究项目，旨在研究由各种环丙烷化芳烃产生的不寻常的碳，而不是传统的来源，如重氮化合物和重氮嘧啶。这些非氮前体提供了一种安全、可行和可替代的碳生成途径。具体项目包括研究α -羟基羰基和新型杂环丙基羰基（包括氧基羰基和氮基羰基羰基）和α -酮羰基的生成，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用于研究。有机和大分子化学项目通过这项本科院校研究奖，支持科尔比学院化学系Dasan M. Thamattoor教授的研究。Thamattoor教授和他的学生们正在通过理论和湿化学来探索被称为碳烯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各样的化学过程中发挥着核心作用，对它们的结构和反应化学的详细了解的发展将导致开发更好的预测工具来控制化学反应性。虽然一些目标碳烯的其他途径是已知的，但Thamattoor教授的研究解决了通过这些其他途径产生的碳烯的结构和反应性的严重问题，此外还为生成新的、以前无法获得的碳烯提供了希望。通过与缅因州教师和学生研究实习（merit）项目的合作，Thamattoor教授将通过包括高中教师和学生来增强该研究项目提供的教育经验。

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.