CAREER: Electron-primed photocatalysis as a platform to expand aryl radical reactions

在化学系化学合成项目的支持下，威斯康星州-麦迪逊大学的Zachary Wickens博士将探索新的方法，使用更可持续的工艺快速合成对制药和农用化学品行业很重要的化合物。Wickens博士和他的团队正在设计一系列催化剂，这些催化剂结合了联合收割机电能和可见光能，在安全、选择性和温和的反应条件下驱动高能量要求的反应。这些研究有望开发出新的反应，用于从廉价的结构单元组装复杂分子，这些结构单元未得到充分利用，因为它们对除了最苛刻的化学试剂之外的所有化学试剂都是惰性的。在这些研究活动的同时，Wickens博士将致力于推进教育和外展计划，通过以学生为中心的教学创新和与当地艺术家的合作来提高有机化学的可及性，以培养社区对科学的兴趣。Zachary Wickens博士和他的研究小组正在开发新的策略，以促进在温和条件下具有挑战性的减少。强还原剂，如碱金属，具有足够的热力学驱动力，以诱导反应性，即使是最还原性的柠檬酸分子;然而，这些试剂通常限于极性反应歧管。相比之下，可见光光氧化还原催化是选择性促进自由基化学的有力策略，但单独来自可见光的能量不足以匹配碱金属的还原电位。Wickens实验室正在努力弥合这一差距，并利用电化学产生持久的自由基阴离子光催化剂，其激发态还原电位远远超过传统的光氧化还原催化。预计这些研究将使以前无法实现的丰富的原料在可持续的条件下进行转化。这些研究活动协同为研究生和本科生提供培训，Wickens博士还开发了一个新的研究生课程，以促进向研究生院的过渡。该奖项反映了NSF的法定使命，并被认为值得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来支持。

With the support of the Chemical Synthesis Program in the Division of Chemistry, Dr. Zachary Wickens of the University of Wisconsin – Madison will explore new ways to rapidly synthesize compounds that are important to the pharmaceutical and agrochemical industries using more sustainable processes. Dr. Wickens and his team are designing a family of catalysts that combine electrical and visible light energy to drive energetically demanding reactions under safe, selective, and mild reaction conditions. These studies are expected to enable the development of new reactions useful for the assembly of complex molecules from inexpensive building blocks that are underutilized because they are inert to all but the harshest chemical reagents. In parallel with these research activities, Dr. Wickens will work to advance educational and outreach initiatives to increase the accessibility of organic chemistry through student-centered teaching innovations and collaborations with local artists to cultivate interest in science among the community. Dr. Zachary Wickens and his research group are developing new strategies to promote thermodynamically challenging reductions under mild conditions. Strong reductants, such as alkali metals, possess a sufficient thermodynamic driving force to induce reactivity from even the most reductively recalcitrant molecules; however, these reagents are typically limited to polar reaction manifolds. In contrast, visible-light photoredox catalysis is a powerful strategy to selectively promote radical chemistry but the energy from visible light alone is insufficient to match the reduction potentials of alkali metals. The Wickens laboratory is working to bridge this gap and using electrochemistry to generate persistent radical anion photocatalysts with excited state reduction potentials far beyond conventional photoredox catalysis. These studies are expected to enable previously inaccessible transformations of abundant feedstocks under sustainable conditions. Synergistically, these research activities are providing training for a diverse cohort of graduate and undergraduate students and Dr. Wickens is also developing a new graduate-level course to facilitate the transition to graduate school.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.