Novel Synthetic Methods

在化学系化学合成项目的支持下，德克萨斯大学达拉斯分校的Vladimir Gevorgyan教授和他的研究生和本科生正在开发温和、高效、选择性的合成有机分子的反应方法。特别是，Gevorgyan小组正在开发有机化学方法，将具有丰富碳氢（C-H）键的现成原料化学品转化为其他更有价值的化学品，这些化学品含有更常见于药物和材料中的新键（碳氧（C-O），碳氮（C-N），碳卤素（C-X），碳碳（C-C），碳硼（C-B）等）。为了实现这些转变，Gevorgyan教授的团队正在开发不使用昂贵且潜在有毒和/或爆炸性试剂的反应方法。除了为构建重要的复杂分子和材料提供新的有效途径外，拟议工作的更广泛影响还包括旨在招募本科生（包括代表性不足的少数民族学生）参与研究的外展活动，从而提高他们的潜力和职业可能性。在这个项目中，Gevorgyan团队正在开发新的温和方法来生成碳中心和杂原子中心的自由基，并解锁它们的反应性。正在开发的方法依赖于能够使用单电子转移（SET）还原亲电中间体的新型供体-受体（DA）配合物。他们的工作是利用可见光引发产生前体自由基，前体自由基经过原子转移（AT）或氢原子转移（HAT）产生转置自由基。这些新的自由基可以参与许多不同的合成转化，包括C(sp3)−H键功能化反应。有利于有效形成DA复合物的因素，以及SET、AT和HAT工艺，将根据该合同进行研究。人们相信，这些方法一旦得到充分发展，不仅会加深我们对电子转移化学的理解，而且还会大大拓宽复杂分子和药物的合成和后期修饰的工具。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 the support of the Chemical Synthesis Program in the Division of Chemistry, Professor Vladimir Gevorgyan and his graduate and undergraduate students at the University of Texas at Dallas are developing mild, efficient, and selective reaction methodology for synthesizing organic molecules. In particular, the Gevorgyan group is developing organic chemistry methodology to convert readily available feedstock chemicals that have an abundance of Carbon–Hydrogen (C–H) bonds into other, more highly valued chemicals that contain new bonds that are more commonly found in medicines and materials (Carbon–Oxygen (C–O), Carbon–Nitrogen (C–N), Carbon–halogen (C–X), Carbon–Carbon (C–C), Carbon–Boron (C–B), etc.). To carry out these transformations, Professor Gevorgyan’s team is developing reaction methodology that is free of costly and potentially toxic and/or explosive reagents. In addition to providing new and effective routes to building complex molecules and materials of importance, the broader impacts of the proposed work include outreach activities that are aimed at recruiting undergraduate students, including underrepresented minority students, into research where their potential and career possibilities will be enhanced.In this project, the Gevorgyan team is developing new mild methods for the generation of carbon- and heteroatom-centered radicals and unlocking their reactivity. The approach under development relies on novel donor-acceptor (DA) complexes capable of the reduction of electrophilic intermediates using single electron transfer (SET). Their work is being carried out using visible light initiation leading to the generation of a precursor radical that undergoes atom transfer (AT) or hydrogen atom transfer (HAT) to generate transposed radicals. These new radicals can then engage in a number of diverse synthetic transformations, including C(sp3)−H bond functionalization reactions. The factors favoring the efficient formation of DA complexes, as well as SET, AT, and HAT processes, will be investigated under this award. It is believed that these methods, when fully developed, will not only deepen our understanding of electron-transfer chemistry, but they will also substantially broaden the tools that are available for the synthesis and late-stage modification of complex molecules and drugs.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.