Computational Study of Reaction Mechanisms for Lithium Carbenoids and Related Species

锂类胡萝卜素及相关物质反应机理的计算研究

• 批准号: 0643629
• 负责人: Lawrence Pratt
• 金额: $ 14万
• 依托单位: Fisk University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-09-01 至 2011-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0643629&HistoricalAwards=false
• 关键词: Computational; Study; Reaction; Mechanisms; Lithium

The Organic and Macromolecular Chemistry Program supports the work of Professor Lawrence Pratt of Fisk University whose research will investigate the reactions of lithium carbenoids, an important class of synthetic reagents. The mode of investigation will be primarily computational quantum chemistry, augmented by experimental methods when necessary. Computational methods are important for research on this class of compounds because experimental studies present many difficulties. Lithium carbenoids are air sensitive and highly reactive, and can often be studied only at low temperatures. Spectroscopic measurements provide clues but cannot, when used alone, elucidate the detailed mechanisms of this class of reactants. Computational quantum chemistry will be used to determine the species that are likely to be present in solution, and to estimate the activation energies of each hypothetical reaction step. Modern quantum methods can estimate these barriers with chemical accuracy, e.g., within one or two kcal/mol. In this way, Professor Pratt will gather a large quantity of data that will allow him to determine which species react, what the reactive intermediates are, if any, and how fast the reactions are likely to occur.This work will result in a better understanding of organic reaction mechanisms. The funding of this work by the Organic and Macromolecular Chemistry Program will result in more efficient methods for organic synthesis, including hard to synthesize natural products that are used by the pharmaceutical industry. Also, an enhanced understanding of the available computational methods and their limitations will result from this work. Broader impacts include the training of undergraduate and masters graduate students in a multicultural and multinational setting. The PI is currently involved in several national and international collaborations, and is expanding these to include universities in Puerto Rico. Fisk University is an HBCU institution with an enrollment of about 70% women. The PI is committed to include other underrepresented minorities in the research projects. The training resulting from this research project will help prepare students to succeed in the global marketplace, and will provide training to prepare students for the job market and the best Ph. D. programs and professional schools.

有机和大分子化学计划支持Fisk University的劳伦斯·普拉特（Lawrence Pratt）教授的工作，其研究将研究锂carbenoids的反应，这是一类重要的合成试剂。研究模式将主要是计算量子化学，必要时通过实验方法增强。计算方法对于研究此类化合物很重要，因为实验研究表现出许多困难。锂类carbenoids是空气敏感和高反应性的，通常只能在低温下进行研究。光谱测量值提供了线索，但在单独使用时不能阐明该类别反应物的详细机制。计算量子化学将用于确定溶液中可能存在的物种，并估算每个假设反应步骤的激活能。现代量子方法可以以化学精度（例如在一两个kcal/mol之内）估算这些障碍。以这种方式，普拉特教授将收集大量数据，使他能够确定哪些物种反应，反应性中间体是什么，如果有的话，以及反应可能发生的速度。这项工作将更好地了解有机反应机制。有机和大分子化学计划对这项工作的资金将导致有机合成的更有效的方法，包括难以合成制药行业使用的天然产品。此外，对可用计算方法及其局限性的增强理解将源于这项工作。更广泛的影响包括在多元文化和跨国环境中培训本科生和硕士研究生。 PI目前参与了几项国家和国际合作，并将其扩展到包括波多黎各的大学。 Fisk University是一家HBCU机构，招收约70％。 PI致力于在研究项目中包括其他代表性不足的少数民族。该研究项目产生的培训将有助于学生在全球市场上取得成功，并将为学生提供培训，使学生为就业市场和最佳博士学位课程和专业学校做好准备。