Zhong Tao, Yi Ji-Tao, Chen Zhi-Da, Zhuang Quan-Can, Li Yong-Zhao, Lu Gui, Weng Jiang
Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University Guangzhou 510006 P. R. China
Chem Sci. 2021 Jun 7;12(27):9359-9365. doi: 10.1039/d1sc02503a. eCollection 2021 Jul 14.
The development of efficient approaches to access sulfonyl fluorides is of great significance because of the widespread applications of these structural motifs in many areas, among which the emerging sulfur(vi) fluoride exchange (SuFEx) click chemistry is the most prominent. Here, we report the first three-component aminofluorosulfonylation of unactivated olefins by merging photoredox-catalyzed proton-coupled electron transfer (PCET) activation with radical relay processes. Various aliphatic sulfonyl fluorides featuring a privileged 5-membered heterocyclic core have been efficiently afforded under mild conditions with good functional group tolerance. The synthetic potential of the sulfonyl fluoride products has been examined by diverse transformations including SuFEx reactions and transition metal-catalyzed cross-coupling reactions. Mechanistic studies demonstrate that amidyl radicals, alkyl radicals and sulfonyl radicals are involved in this difunctionalization transformation.
由于磺酰氟结构基序在许多领域的广泛应用，开发高效获取磺酰氟的方法具有重要意义，其中新兴的硫（VI）氟交换（SuFEx）点击化学最为突出。在此，我们报道了通过将光氧化还原催化的质子耦合电子转移（PCET）活化与自由基接力过程相结合，首次实现未活化烯烃的三组分氨基氟磺酰化反应。在温和条件下，以良好的官能团耐受性高效地得到了各种具有特殊五元杂环核心的脂肪族磺酰氟。通过包括SuFEx反应和过渡金属催化的交叉偶联反应在内的多种转化，研究了磺酰氟产物的合成潜力。机理研究表明，酰胺基自由基、烷基自由基和磺酰基自由基参与了这种双官能化转化。
