New Chemistry Enabled by Aryne Intermediates

化学部化学合成计划支持李大成教授的项目。李教授是伊利诺伊大学芝加哥分校化学系的教员。他正在开发利用被称为芳烃的高活性化合物的新类别的合成转化。Arynes它们的化学键中有足够的内部能量，使合成高应变的四元环结构成为可能，这些结构通常用于制造药物、生物活性天然产品的分子支架和其他功能材料。李教授正在利用一种既定的反应，仔细地组装绑在诱捕群上的芳烃。该项目包括合成方法开发、机理研究和天然产物合成。李教授的团队处于有利地位，可以为各种各样的学生提供高水平的教育和培训。本科生和高中生的暑期研究实习是该项目的一部分。这项研究通过为化学工业和医药提供创新并产生一支受过高度技术培训的劳动力而造福于社会。芳炔类化合物相对较高的亲电性以及它们与过渡金属络合物相互作用的倾向为探索新的反应活性提供了一个通用的平台。这项研究集中在银络合芳烃中间体的高反应性所实现的新的转化，这使得各种四元环结构的形成成为可分离的产物或作为过渡中间体。具体的研究领域包括探索芳烃依靠空间效应和氢键元素进行的四元环形成Alder-ene反应，研究使用各种芳烃-烯中间体进行Alder-ene和[2+2]环加成反应的化学和区域选择性，以及它们在合成除草剂B中的应用。Lee教授还考虑开发一种新的合成方法来构建依赖于芳烃-羰基[2+2]环加成反应的色满酮衍生物，以及芳烃与碳-氮多键的新环合反应，以生成新型杂环芳香族化合物。用于过渡金属催化转化的苯环丁烯衍生物的探索也在研究中。该教育计划包括一项面向高中生的暑期研究计划，向他们介绍合成有机化学。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。

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Daesung Lee. Professor Lee is a faculty member in the Department of Chemistry at the University of Illinois at Chicago. He is developing new classes of synthetic transformations that take advantage of highly reactive chemical compounds known as arynes. Arynes they have enough internal energy in their chemical bonds to enable the synthesis of highly strained, four-membered cyclic structures that are often used to make pharmaceuticals, molecular scaffolds for bioactive natural products, and other functional materials. Professor Lee is using an established reaction to carefully assemble arynes that are tethered to trapping groups. The project includes synthetic method development, mechanistic studies, and natural product synthesis. Professor Lee's group is well positioned to provide a high level of education and training for a wide variety of students. A summer research internship for undergraduate and high school students is part of the project. This research benefits society by providing innovations to the chemical industry and medicine and by producing a highly technically-trained workforce.The relatively high electrophilic nature of arynes in combination with their tendency to interact with transition metal complexes provide a versatile platform for exploring new reactivity. This research focuses on novel transformations enabled by the high reactivity of silver-complexed aryne intermediates, which allows for the formation of a variety of four-membered ring structures as isolable products or as transient intermediates. Specific areas of research involve the exploration of four-membered ring-forming Alder-ene reaction by arynes relying on steric effect and hydrogen bonding elements and an investigation of chemo- and regioselectivity for Alder-ene and [2+2] cycloadditions employing various aryne-allene intermediates, and their application for the synthesis of herbindole B. Professor Lee also considers the development of a new synthetic method for the construction of chromanone derivatives relying on the aryne-carbonyl [2+2] cycloaddition reactions and of new annulation reactions of arynes with carbon-nitrogen multiple bonds to form novel heteroaromatic compounds. Exploration of benzocyclobutene derivatives for transition metal-catalyzed transformations is also under study. The educational plan includes a summer research program for high school students to introduce them to synthetic organic chemistry.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.