Novel Synthetic Methods

在化学系化学合成计划的支持下，Vladimir Gevorgyan教授和他在达拉斯的德克萨斯大学的研究生和本科生正在开发温和、高效和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，将容易获得的具有丰富碳氢(C-H)键的原料化学品转化为其他更有价值的化学品，这些化学品含有药品和材料中更常见的新键(碳-氧(C-O)、碳-氮(C-N)、碳-卤素(C-X)、碳-碳(C-C)、碳-硼(C-B)等)。为了进行这些转化，Gevorgyan教授的团队正在开发不含昂贵和潜在有毒和/或爆炸性试剂的反应方法。除了提供构建复杂分子和重要材料的新的有效途径外，拟议工作的更广泛影响包括旨在招募本科生(包括未被充分代表的少数族裔学生)参与研究的外联活动，在这些研究中，他们的潜力和职业可能性将得到增强。在这个项目中，Gevorgyan团队正在开发新的温和方法来生成以碳和杂原子为中心的自由基，并释放它们的反应性。正在开发的方法依赖于新型的给体-受体(DA)络合物，能够通过单电子转移(SET)还原亲电中间体。他们的工作是利用可见光引发产生前体自由基，该自由基经历原子转移(AT)或氢原子转移(HAT)来产生转置自由基。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键官能化反应。有利于DA复合体有效形成的因素以及SET、AT和HAT过程将在本奖项下进行调查。人们相信，当这些方法完全发展时，不仅将加深我们对电子转移化学的理解，而且它们还将极大地拓宽可用于复杂分子和药物的合成和后期修饰的工具。该奖项反映了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, 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.