Mechanisms and Application of Dehydro-Diels-Alder Cycloadditions

通过这个奖项，美国国家科学基金会化学部的化学合成项目支持了匹兹堡大学化学系Kay Brummond教授的研究。Brummond教授和她的小组正在与刘鹏教授小组合作，使用实验和计算相结合的方法研究脱芳香脱氢- diels - alder （DDDA）反应。阐明在这些转化中发生的键重组的细节是很重要的，这样化学家们就能更好地合理地扩大反应的普遍性。从应用的角度来看，这种化学反应也具有很大的价值，因为可预测的DDDA化学反应允许控制产品的结构特征，这些结构特征是这些系统所需物理性质的基础。这些研究的结果正被应用于设计新的策略，以制备具有社会重要性的新型化合物，特别是高性能有机光伏材料。这种合作方式为下一代科学问题解决者和传播者提供了丰富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。Brummond教授还将下一代化学家的培训和指导与自上而下的方法结合起来，在系和学院层面实施多样性、公平和包容性战略，为扩大科学、技术、工程和数学（STEM）中代表性不足的群体的参与提供一个深远而强大的平台。脱氢- diels - alder反应是制备高不饱和六元环的有效方法；然而，当这些反应涉及到杂芳烃的脱芳化时，苛刻的条件和多种产物的形成会损害它们的用途。Brummond教授和她的研究小组正在通过确定控制杂环芳烃反应活性和产物选择性的因素，努力提高脱芳香脱氢- diels - alder （DDDA）反应的合成效用。实验和计算机制研究正在同时进行，以系统地建立电子和立体趋势，并提高计算可靠性。计算研究正在与同样在匹兹堡大学的刘鹏教授的研究小组合作进行。通过合成新型梯型杂芳烃化合物，也扩大了DDDA反应的合成用途。从这些阶梯型共轭结构中设计和合成高性能有机光伏材料的聚合方法正在开发中，这将为交叉耦合方法提供有价值的替代方法。目标选择过程由有机电子材料理论建模和模拟专家进行的计算特性预测指导。Brummond教授致力于通过增加化学和自然科学领域的多样性，公平性和包容性（DEI）来扩大STEM的参与，使用的方法既包括自下而上的方法，保持一个活跃的研究小组，专注于为下一代有机化学家提供咨询和指导，也包括自上而下的方法，利用她作为学术领袖和Kenneth P. Dietrich艺术与科学学院副院长的地位。支持以证据为基础的战略，改变文化、政策和实践，缩小科学领域的DEI差距。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.