Radical Trifluoromethyl- and Perfluoroalkylation via Reductive and Oxidative Processes

通过还原和氧化过程进行自由基三氟甲基化和全氟烷基化

• 批准号: 223531595
• 负责人: Professor Dr. Armido Studer
• 金额: --
• 依托单位: Organisch-Chemisches Institut
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/223531595?language=en
• 关键词: Radical; Trifluoromethyl; Perfluoroalkylation; via; Reductive

In the second project period new fluorinated Togni-type I(III)-reagents will be developed and used as C-radical precursors for the mild introduction of functionalized fluorinated alkyl groups into various pi-systems (alkenes, arenes and alkynes). Reactions will be mediated by mild organic single electron reductants such as TEMPONa. In addition, organic dianions will be tested as single electron transfer reducing reagents for clean C-radical generation in the reaction with I(III)-reagents. Cross-coupling of longer-lived radical anions with short-lived perfluoroalkyl radicals will be investigated. In these processes the concept of the Persistent Radical Effect will be applied. In addition, a method for phenol O-trifluoromethylation, which is an unsolved problem in synthesis, will be developed. Finally, oxidative radical trifluoromethylation and trifluoromethylthiolation will be explored.

在第二个项目期间，将开发新的氟化Togni I（III）型试剂，并将其用作C-自由基前体，用于将官能化氟化烷基温和地引入各种π-体系（烯烃，芳烃和炔）。反应将由温和的有机单电子还原剂如TEMPONa介导。此外，有机二价阴离子将作为单电子转移还原剂进行测试，以在与I（III）-试剂的反应中产生清洁的C-自由基。将研究长寿命自由基阴离子与短寿命全氟烷基自由基的交叉偶联。在这些过程中，将应用持久性自由基效应的概念。此外，苯酚O-三氟甲基化的方法，这是一个尚未解决的合成问题，将开发。最后，将探讨氧化自由基三氟甲基化和三氟甲基硫醇化。

项目成果

Site-Selective Remote Radical C-H Functionalization of Unactivated C-H Bonds in Amides Using Sulfone Reagents.

• DOI: 10.1002/anie.201807455
• 发表时间: 2018-08
• 期刊: Angewandte Chemie
• 作者: Yong Xia;Lin Wang;A. Studer

Sodium-Ketyl Radical Anions by Reverse Pinacol Reaction and Their Coupling with Iodoarenes.

逆频哪醇反应生成钠-酮基阴离子及其与碘芳烃的偶联

• DOI: 10.1021/acs.orglett.6b02184
• 发表时间: 2016
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: X. Tang;A. Studer
• 通讯作者: A. Studer