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

在化学系化学合成计划的支持下，威斯康星大学麦迪逊分校的Zachary Wkins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化行业重要的化合物。威肯斯博士和他的团队正在设计一系列催化剂，将电能和可见光能量结合在一起，在安全、选择性和温和的反应条件下驱动能量要求高的反应。这些研究有望从廉价的积木中开发出有助于组装复杂分子的新反应，这些积木没有得到充分利用，因为它们对除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，威肯斯博士将致力于推进教育和推广活动，通过以学生为中心的教学创新和与当地艺术家的合作，增加有机化学的可及性，培养社区对科学的兴趣。Zachary Wkins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热力学挑战性的减排。强还原剂，如碱金属，具有足够的热力学驱动力，即使是最难还原的分子也能引发反应；然而，这些试剂通常仅限于极性反应流形。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一种有效策略，但仅靠可见光的能量不足以与碱金属的还原电位相匹配。威肯斯实验室正致力于弥补这一差距，并利用电化学方法生成具有激发态还原潜力的持久性自由基阴离子光催化剂，远远超过传统的光氧化还原催化。这些研究可望在可持续的条件下实现以前无法获得的丰富原料的转化。协同作用，这些研究活动正在为不同的研究生和本科生提供培训，威肯斯博士还开发了一门新的研究生课程，以促进向研究生院的过渡。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.