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.

实际上，从含氮前体获得的碳样产物实际上可能来自前体本身的激发态。此外，许多氮前体可能会危害处理或根本无法合成以产生感兴趣的卡宾人 - 例如，目前不可用的一种方便且广泛适用的方法是生成A-羟基碳苯甲部的一种。该提案描述了一项面向大学的研究计划，旨在研究由各种环丙烷芳香剂而不是常规来源（例如重氮化合物和重氮素）产生的异常卡宾。这些非硝基源前体为卡宾产生提供了安全，可行的替代途径。特定项目包括研究A-羟基碳烯和新型的杂丙基碳苯甲酸（包括氧甲酰基和副偶氮素碳苯甲酸）以及生成A-酮碳烯，以解决沃尔夫重排过程中的关键机制问题。电子自旋谐振光谱，时间分辨激光闪光光解和先进的计算方法也将进行研究。在本科机构奖的这项研究中，有机和大分子化学计划支持科尔比学院化学系的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，被称为Carbenes的不寻常电子的物种的制备，结构和反应性探索。这些不寻常的物种在各种化学过程中起着核心作用，对它们的结构和反应化学的详细理解将导致开发更好的预测性工具来控制化学反应性。尽管已知到一些靶向卡宾人的其他路线是众所周知的，但Thamattoor教授的研究涉及有关通过这些其他途径产生的卡宾人的结构和反应性的严重问题，此外，还提供了有望产生新的，以前不可用的卡宾斯。通过与缅因州的教师和学生研究实习（绩效）计划的合作，Thamattoor教授将通过包括高中教师和学生在内，增强该研究计划提供的教育经验。