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

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是危险的，或者可能根本不能合成用于产生感兴趣的卡宾-例如，目前还没有一种方便和广泛适用的生成α-羟基卡宾的方法。该提案描述了一个面向本科生的研究计划，旨在研究从各种环丙烷化芳烃而不是传统的来源，如重氮化合物和二氮杂环丙烷产生的不寻常的卡宾。这些不含氮的前体提供了一种安全、可行和替代的卡宾生成途径。具体项目包括研究α-羟基卡宾和新的杂环丙基卡宾（包括环氧乙烷基和氮丙啶基卡宾），以及生成α-酮基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，和先进的计算方法将承担的调查以及。有了这个研究在本科院校奖，有机和高分子化学计划支持教授Dasan M。科尔比学院化学系的Thamattoor说。Thamattoor教授和他的学生正在探索，通过理论和湿化学，制备，结构和不寻常的缺电子物种被称为卡宾的反应性。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将有助于开发更好的预测工具来控制化学反应性。虽然已知一些目标卡宾的其他途径，但Thamattoor教授的研究解决了关于通过这些其他途径产生的卡宾的结构和反应性的严重问题，并为新的，以前不可用的卡宾的产生提供了希望。通过与缅因州教师和学生研究实习（MERITS）计划的合作伙伴关系，教授Thamattoor将通过包括高中教师和学生来增强本研究计划提供的教育经验。

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.