Mechanisms and Application of Dehydro-Diels-Alder Cycloadditions

脱氢-Diels-Alder环加成反应机理及应用

• 批准号: 1956024
• 负责人: Kay Brummond
• 金额: $ 49万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1956024&HistoricalAwards=false
• 关键词: Mechanisms; Application; Dehydro; Diels; Alder

With this award, the Chemical Synthesis Program of the NSF Division of Chemistry is supporting the research of Professor Kay Brummond at the Department of Chemistry, University of Pittsburgh. Professor Brummond and her group are studying dearomative dehydro-Diels-Alder (DDDA) reactions using a combined experimental and computational approach in collaboration with the group of Professor Peng Liu. Elucidating details of the bond reorganization that occurs in these transformations is important so that chemists are better able to rationally expand the generality of the reaction. This chemistry is also of great value from an applications standpoint as predictable DDDA chemistry allows for control of the structural characteristics of the product that underlie the desirable physical properties of these systems. The findings from these investigations are being applied to the design of new strategies for preparing novel compounds of societal importance, in particular, high-performing organic photovoltaic materials. The collaborative approach is affording the next-generation of scientific problem-solvers and communicators equipped with a breadth of experience and chemical expertise to ask the right questions and provide innovative solutions. Professor Brummond is also combining training and mentoring of next generation of chemists with a top-down approach to implement diversity, equity, and inclusivity strategies at the departmental and college level, to provide a far-reaching and powerful platform for broadening participation of underrepresented groups in science, technology, engineering, and mathematics (STEM). The dehydro-Diels–Alder reaction is a powerful method for preparing highly unsaturated six-membered rings; however, when these reactions involve the dearomatization of a heteroarene, harsh conditions and the formation of multiple products compromise their usefulness. Professor Brummond and her research group are working to improve the synthetic utility of dearomative dehydro-Diels–Alder (DDDA) reactions by determining factors that control reactivity and product selectivity for heteroarenes. Both experimental and computational mechanistic studies are being performed in tandem to systematically establish electronic and steric trends, as well as increase computational reliability. Computational studies are being done in collaboration with the research group of Professor Peng Liu, also at the University of Pittsburgh. Expansion of the synthetic utility of the DDDA reaction is also being achieved through the synthesis of novel ladder-type heteroarene compounds. Convergent methods to design and synthesize high performing organic photovoltaic materials from these ladder-type conjugated structures are being developed and will provide valuable alternatives to cross-coupling approaches. The target selection process is being guided by computational property predictions performed by an expert in theoretical modeling and simulation of organo-electronic materials. Professor Brummond is committed to broadening participation in STEM by increasing diversity, equity, and inclusivity (DEI) in chemistry specifically and in the natural sciences using methodology that incorporates both a bottom-up approach, maintaining an active research group focused on advising and mentoring the next generation of organic chemists, and a top-down approach, leveraging her position as an academic leader and associate dean for the Kenneth P. Dietrich School of Arts and Sciences, to champion evidence-based strategies to change culture, policies, and practices to close DEI gaps in the sciences.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

通过此奖项，NSF化学部的化学合成计划支持匹兹堡大学化学系教授的研究。 Brummond教授和她的小组正在研究与Peng Liu教授合作的合并实验和计算方法，使用合并的实验和计算方法来研究Dearomative Dehydro-Diels-Alder（DDDA）反应。阐明这些转化中发生的键重组的细节很重要，因此化学家可以更好地扩大反应的一般性。从应用的角度来看，这种化学也具有很大的价值，因为可预测的DDDA化学允许控制这些系统所需物理特性的产品的结构特征。这些投资的发现应用于设计新策略，以准备新的社会重要性化合物，尤其是高性能的有机光伏材料。协作方法是为科学问题和沟通者提供了下一代，配备了广泛的经验和化学专业知识，以提出正确的问题并提供创新的解决方案。布鲁蒙德教授还将下一代化学家的培训和心理化与在部门和大学一级实施多样性，公平和包容性策略的自上而下的方法相结合，提供了一个宽深而有力的平台，以扩大代表性不足的科学，技术，工程，工程和数学（STEM）中代表性不足的团体的参与。脱氢型 - 阿尔德反应是制备高度不饱和六元环的有力方法。但是，当这些反应涉及异烯烯的珍爱，危害条件和多种产品的形成会损害其有用性。 Brummond教授和她的研究小组正在努力通过确定控制异芳族的反应性和产品选择性的因素，以改善脱氢脱氢型二烷 - alder（DDDA）反应的合成效用。实验和计算机械研究都在同时进行系统地建立电子和空间趋势，并提高计算可靠性。与匹兹堡大学的彭刘教授的研究小组合作进行了计算研究。通过合成新型的梯子型异烯化合物，还可以实现DDDA反应的合成效用的扩展。从这些梯子型连接的结构中设计和合成高性能的有机光伏材料的收敛方法正在开发，并将为交叉耦合方法提供宝贵的替代方法。目标选择过程是由有机电子材料的理论建模和模拟专家进行的计算属性预测来指导的。布朗蒙德教授致力于通过提高化学方面的多样性，公平和包容性（DEI），并在自然科学中提高多样性，公平性和包容性（DEI）来扩大STEM的参与。倡导基于证据的策略来改变文化，政策和实践，以弥合科学中的DEI差距。该奖项反映了NSF的法定使命，并使用基金会的知识分子优点和更广泛的影响审查标准，通过评估被认为是宝贵的支持。