Expanding the Fundamental Reactivity of Isocyanides

扩大异氰化物的基本反应活性

• 批准号: 1953128
• 负责人: Fraser Fleming
• 金额: $ 49万
• 依托单位: Drexel University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-10-01 至 2024-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1953128&HistoricalAwards=false
• 关键词: Expanding; Fundamental; Reactivity; Isocyanides

With this award, the Chemical Synthesis Program of the NSF Division of Chemistry is supporting the research of Professor Fraser Fleming of the Department of Chemistry at Drexel University who is developing new ways to make and use a chemical building block called an isocyanide. Key goals of this project are to prepare more examples of unique types of isocyanides and to increase the number of ways isocyanides are used to form molecules. Currently, there are only seven examples of commercially available isocyanides, which limits the number of compounds that can be made with these building blocks. This program is creating simple ways to make more isocyanides and to use them to form new desirable molecules for pharmaceutical and material applications. Professor Fleming works with a diverse group of graduate and undergraduate students and is leading student retreats focused on work-life balance to ensure that future leaders learn the practices required for high-performing leadership in the chemical industry. Isocyanides are valuable linchpins for assembling heterocycles and peptidomimetics, which are privileged structures in material and medicinal applications. A major limitation to the implementation of isocyanides for accessing these desirable products is that there are only seven commercially available examples. This research program is working expand these systems by designing new reactions that form more complex examples of these important building blocks and increase the types of bond connections that isocyanides can be used to prepare. Specifically, this project is designing methods for: alkenyl isocyanides to undergo conjugate addition reactions, aryl isocyanides to participate in multicomponent processes to form complex heterocycles, and boroalkylisocyanides to be prepared and used in cross coupling reactions to form more complex isocyanide products. This research program also serves as an excellent training ground for graduate and undergraduate researchers who are also participating in retreats to hone their work-life balance skills and to prepare for future leadership roles in chemistry careers.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.

凭借该奖项，美国国家科学基金会化学部的化学合成计划正在支持德雷克塞尔大学化学系弗雷泽·弗莱明教授的研究，该教授正在开发制造和使用一种称为异氰化物的化学构件的新方法。该项目的主要目标是准备更多独特类型异氰化物的示例，并增加异氰化物用于形成分子的方式数量。目前，市售异氰化物只有七个例子，这限制了用这些结构单元可以制造的化合物的数量。该计划正在创造简单的方法来制造更多的异氰化物，并使用它们来形成用于制药和材料应用的新的理想分子。弗莱明教授与多元化的研究生和本科生群体合作，并领导学生静修会，重点关注工作与生活的平衡，以确保未来的领导者学习化学行业高绩效领导力所需的实践。异氰化物是组装杂环和肽模拟物的重要关键，它们是材料和医学应用中的特权结构。使用异氰化物来获得这些理想产品的一个主要限制是，只有七个商业可用的例子。该研究计划正在通过设计新的反应来扩展这些系统，这些新的反应形成这些重要构建单元的更复杂的例子，并增加异氰化物可用于制备的键连接的类型。具体来说，该项目正在设计以下方法：烯基异氰化物进行共轭加成反应，芳基异氰化物参与多组分过程形成复杂的杂环，以及硼烷基异氰化物制备并用于交叉偶联反应以形成更复杂的异氰化物产物。该研究项目还为研究生和本科生研究人员提供了绝佳的培训基地，他们也参加了静修活动，以磨练工作与生活平衡技能，并为未来在化学职业中的领导角色做好准备。该奖项反映了 NSF 的法定使命，并被视为值得通过使用基金会的智力优点和更广泛的影响审查标准进行评估来支持。

项目成果

Interrupted S N Ar-Alkylation Dearomatization

间断SN Ar烷基化脱芳构化

• DOI: 10.1021/jacsau.3c00813
• 发表时间: 2024-02
• 期刊: JACS Au
• 影响因子: 8
• 作者: Altundas, Bilal;Marrazzo, John;Brinck, Tore;Absil, Christopher;Fleming, Fraser F.
• 通讯作者: Fleming, Fraser F.

Metalated isocyanides: formation, structure, and reactivity

金属化异氰化物：形成、结构和反应性

• DOI: 10.1039/d0ob01340d
• 发表时间: 2020-08
• 期刊: Organic & Biomolecular Chemistry
• 影响因子: 3.2
• 作者: Altundas, Bilal;Marrazzo, John;Fleming, Fraser F.
• 通讯作者: Fleming, Fraser F.

Polar-Radical Cyclization Cascades with Magnesiated Nitriles

与镁化腈的极性自由基环化级联

• DOI: 10.1021/acs.orglett.3c01094
• 发表时间: 2023-05
• 期刊: Organic Letters
• 影响因子: 5.2
• 作者: Bolgunas, Stephen;Paleo, Ehecatl;Alwedi, Embarek;Wei, Yunjing;Keller, Taylor M.;Fleming, Fraser F.
• 通讯作者: Fleming, Fraser F.

Stereoselective Synthesis of ( E )- and ( Z )-Isocyanoalkenes

(E)-和(Z)-异氰基烯烃的立体选择性合成

• DOI: 10.1021/acs.orglett.2c03461
• 发表时间: 2022-12
• 期刊: Organic Letters
• 影响因子: 5.2
• 作者: Tian, Huan;Holyoke, Caleb W.;Fleming, Fraser F.
• 通讯作者: Fleming, Fraser F.

Oxidative DMSO Cyclization Cascade to Bicyclic Hydroxyketonitriles

氧化 DMSO 环化级联生成双环羟基酮腈

• DOI: 10.1021/acs.joc.2c00364
• 发表时间: 2022-05
• 期刊: The Journal of Organic Chemistry
• 作者: Kornfeind, John;Iyer, Pravin S.;Keller, Taylor M.;Fleming, Fraser F.
• 通讯作者: Fleming, Fraser F.