权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Synthesis via Decarboxylative Activation

通过脱羧活化合成

基本信息

批准号：
1800147
负责人：
Jon Tunge
金额：
$ 45万
依托单位：
University of Kansas Center for Research Inc
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-08-01 至 2022-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800147&HistoricalAwards=false
关键词：
Synthesis via Decarboxylative Activation

项目摘要

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Tunge. Professor Tunge is a faculty member in the Department of Chemistry at The University of Kansas. He is developing new classes of reactions that are less harmful to the environment than current state-of-the-art technologies. To do this, Professor Tunge and his group harness the chemical potential inherent in carboxylic acids. These groups are very common and can be found in a wide variety of readily available, renewable materials. By developing methods that take advantage of carboxylic acids, the Tunge group is able to convert these readily available materials into more valuable chemicals. This is accomplished by the novel combination of two types of chemical reagents that in turn lowers the energy barrier to reactions that were previously unavailable. This leads to new types of chemical reactivity. In the specific project being pursued the carboxylic acid is stripped out of the molecule to form a highly reactive intermediate that can then be used to generate new chemical bonds. In addition to its scientific value, this combination of environmentally friendly reagents to achieve synthetic goals provides an excellent vehicle for training students to make chemicals and materials in a wide variety of industries. Professor Tunge's group is also engaged in scientific outreach in catalysis education and is developing new avenues for recruitment of underrepresented groups into the chemistry profession. Carboxylic acids are a ubiquitous, often renewable source of organic reactants. Past chemistries have allowed the Tunge group to transform carboxylic acids into a variety of chemicals using decarboxylation to form reactive nucleophiles (pKa 10-32). In this project, carboxylic acids are being combined with transition metal catalysts in combination with photoredox catalysts to form reactive nucleophiles of high basicity (pKa 32-48), thus obviating the need for stoichiometric organometallic reagents. In addition to using carboxylic acids as carbanion equivalents, new strategies are being developed that allow decarboxylation to be used to generate radical and carbocation intermediates. Ultimately, these studies are being employed to determine optimal conditions for generating specific reactive intermediates and then exploiting those intermediates through C-C bond forming, elimination, and nucleophilic trapping reactions. This chemistry integrates the themes of catalysis with green chemistry and synthesis. These themes are further emphasized in educational materials related to catalysis that are broadly disseminated online.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.

化学部化学合成计划支持通格教授的项目。汤格教授是堪萨斯大学化学系的一名教员。他正在开发新的反应类别，这些反应对环境的危害比目前最先进的技术要小。为了做到这一点，通格教授和他的团队利用了羧酸固有的化学势。这些基团非常常见，可以在各种随时可用的可再生材料中找到。通过开发利用羧酸的方法，Tunge团队能够将这些容易获得的材料转化为更有价值的化学品。这是通过两种类型的化学试剂的新颖组合实现的，这反过来又降低了以前无法获得的反应的能量屏障。这导致了新类型的化学反应。在正在进行的具体项目中，羧酸被从分子中剥离出来，形成一种高活性的中间体，然后可以用来产生新的化学键。除了它的科学价值，这种实现合成目标的环境友好型试剂的组合为培训学生在各种行业制造化学品和材料提供了一个极好的工具。Tunge教授的团队还致力于催化教育的科学推广，并正在开发新的途径，以招募代表不足的群体进入化学专业。羧酸是一种无处不在的、通常可再生的有机反应物来源。过去的化学反应允许Tunge组使用脱羧基将羧酸转化为各种化学物质，以形成活性亲核剂(PKA 10-32)。在这个项目中，羧酸与过渡金属催化剂和光氧化还原催化剂结合在一起，形成高碱性的活性亲核剂(pKa 32-48)，从而消除了对化学计量比有机金属试剂的需要。除了使用羧酸作为碳负离子的等价物外，正在开发新的策略，允许脱羧基用于生成自由基和碳正离子中间体。最终，这些研究将被用来确定产生特定活性中间体的最佳条件，然后通过C-C键的形成、消除和亲核捕获反应来利用这些中间体。这门化学将催化、绿色化学和合成的主题结合在一起。这些主题在网上广泛传播的与催化有关的教育材料中得到了进一步的强调。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。