New Synthetic Opportunities with N-Alkenylnitrones and N,O-Dialkenylhydroxylamines

凭借该奖项，美国国家科学基金会化学部的化学合成项目正在支持伊利诺伊大学芝加哥分校 (UIC) 劳拉·L·安德森 (Laura L. Anderson) 教授的研究，开发构建分子的新方法，以帮助满足社会对新药物和新材料的需求。安德森教授与研究生和本科生合作，设计使用一种称为硝酮的反应分子作为廉价、容易获得的试剂和复杂的增值化合物之间的关键的方法。这些硝酮关键分子针对新的化学键结构进行了调整。正在确定可靠的路线以轻松生成关键中间体。这种方法提供了用于制药和农业应用的理想化合物的新例子。这项工作的更广泛影响源于新反应产生的化合物，以及确定的新策略和基本反应模式。该项目的教育方面旨在培训有抱负的研究生和本科生化学家，以及夏季参与该项目的高中生。 UIC 是一所少数族裔服务机构，该项目的额外社会效益包括招募和参与各级代表性不足的学生。Anderson 教授和她的学生设计了共轭硝酮中间体的聚合合成路线，以及这些中间体在合成新型杂环中的不同立体控制应用。该计划的总体目标是将两种简单的起始材料结合起来以获得新颖的反应性中间体，然后调整这些中间体的反应性，以通过少量步骤制备一系列增值产品。共轭硝酮中间体的反应性目标包括确定如何控制氮杂环丁烷不对称合成的电环化反应的立体选择性，以及设计引导级联过程合成螺环吡咯啉的方法。改善共轭硝酮中间体的获取的目的包括识别和修复肟的 Chan-Lam 反应中的障碍。由于已确定的基本反应模式和合成策略，以及通过获得新的杂环化合物而实现的化学空间的扩展，这些活动产生了更广泛的影响。教育目标是通过培训一群研究生、本科生和高中生进行分析性思考、磨练解决问题的能力以及获得 STEM 学科的实践经验来实现的。代表性不足的群体的参与进一步通过促进多样性来改善化学的未来。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力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 Laura L. Anderson at the University of Illinois at Chicago (UIC) to develop new ways to construct molecules to help meet society's demands for new drugs and new materials. Professor Anderson works with graduate and undergraduate students designing ways to use a reactive molecule called a nitrone as the lynchpin between cheap, readily-accessible reagents and complicated value-added compounds. These nitrone lynchpins are tuned towards new chemical bond construction. Robust routes are being determined to easily generate key intermediates. This approach provides access to new examples of desirable compounds for pharmaceutical and agricultural applications. The broader impact of this work results from both the compounds generated from the new reactions, as well as the new strategies and fundamental reactivity patterns that are identified. Educational aspects of the project are aimed towards training aspiring chemists at the graduate and undergraduate level, as well as high school students that participate in the project over the summer. UIC is a minority serving institution and additional societal benefits of this program include the recruitment and participation of under-represented students at all levels.Professor Anderson and her students design convergent synthetic routes to conjugated nitrone intermediates and divergent stereocontrolled applications of these intermediates for the synthesis of novel heterocycles. The overarching goal of this program is to couple two simple starting materials to access novel reactive intermediates and then to tune the reactivity of these intermediates to prepare an array of value-added products in a small number of steps. Reactivity goals for the conjugated nitrone intermediates include determining how to control the stereoselectivity of an electrocyclization reaction for the asymmetric synthesis of azetidines and designing ways to direct a cascade process towards the synthesis of spirocyclic pyrrolines. The aim of improving access to conjugated nitrone intermediates involves identifying and fixing road blocks in the Chan-Lam reactions of oximes. These activities provide impact on a broader scale due to the fundamental reactivity patterns and synthetic strategies that are identified, as well as the expansion of chemical space that is achieved through access to new heterocyclic compounds. Educational goals are achieved by training a group of graduate, undergraduate, and high school students to think analytically, hone their problem-solving skills, and have hands-on experience with a STEM discipline. The involvement of underrepresented groups further serves to better the future of chemistry through advancing diversity.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.