Li Guo-Qing, Li Zi-Qing, Jiang Min, Zhang Zhihan, Qian Yu, Xiao Wen-Jing, Chen Jia-Rong
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079, China.
College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036, China.
Angew Chem Int Ed Engl. 2024 Aug 5;63(32):e202405560. doi: 10.1002/anie.202405560. Epub 2024 Jul 9.
Radical-involved multicomponent difunctionalization of 1,3-dienes has recently emerged as a promising strategy for rapid synthesis of valuable allylic compounds in one-pot operation. However, the expansion of radical scope and enantiocontrol remain two major challenges. Herein, we describe an unprecedented photoinduced copper-catalyzed highly enantioselective three-component radical 1,2-azidooxygenation of 1,3-dienes with readily available azidobenziodazolone reagent and carboxylic acids. This mild protocol exhibits a broad substrate scope, high functional group tolerance, and exceptional control over chemo-, regio- and enantioselectivity, providing practical access to diverse valuable azidated chiral allylic esters. Mechanistic studies imply that the chiral copper complex is implicated as a bifunctional catalyst in both the photoredox catalyzed azidyl radical generation and enantioselective radical C-O cross-coupling.
1,3-二烯的涉及自由基的多组分双官能团化反应最近已成为一种很有前景的策略，可通过一锅法快速合成有价值的烯丙基化合物。然而，自由基范围的扩展和对映体控制仍然是两个主要挑战。在此，我们描述了一种前所未有的光诱导铜催化的1,3-二烯与易于获得的叠氮苯并碘二唑酮试剂和羧酸的高度对映选择性三组分自由基1,2-叠氮氧基化反应。这种温和的方法具有广泛的底物范围、高官能团耐受性以及对化学、区域和对映选择性的出色控制，为获得各种有价值的叠氮基手性烯丙基酯提供了实用途径。机理研究表明，手性铜配合物在光氧化还原催化的叠氮基自由基生成和对映选择性自由基C-O交叉偶联中均作为双功能催化剂起作用。
