Yu Jiajia, Wu Zhen, Zhu Chen
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China.
Angew Chem Int Ed Engl. 2018 Dec 21;57(52):17156-17160. doi: 10.1002/anie.201811346. Epub 2018 Nov 27.
Radical-mediated difunctionalization of alkenes is a powerful tactic for olefin utilization. However, the transformation of unactivated alkenes still remains a formidable challenge. Now a conceptually new docking-migration strategy is presented for the difunctionalization of alkenes with photoredox catalysis. Both activated and unactivated alkenes are suitable substrates. A vast array of functional groups are compatible with the mild reaction conditions. Heteroaryl and difluoromethyl are concomitantly incorporated into alkenes, leading to synthetically valuable products that are readily converted into a variety of fluorine-containing molecules. The protocol provides a kinetic control of stereoselectivity for cycloalkenes to generate the unusual cis-products, and offers an efficient approach for the late-stage functionalization of complex natural products and drug molecules. A portfolio of dual-function reagents are prepared for the elusive radical difunctionalization of alkenes.
自由基介导的烯烃双官能团化是一种强大的烯烃利用策略。然而，未活化烯烃的转化仍然是一项艰巨的挑战。现在提出了一种概念上全新的对接-迁移策略，用于光氧化还原催化的烯烃双官能团化。活化和未活化的烯烃都是合适的底物。大量官能团与温和的反应条件兼容。杂芳基和二氟甲基同时引入烯烃中，生成具有合成价值的产物，这些产物很容易转化为各种含氟分子。该方案为环烯烃提供了立体选择性的动力学控制，以生成不寻常的顺式产物，并为复杂天然产物和药物分子的后期官能团化提供了一种有效方法。制备了一系列双功能试剂，用于难以捉摸的烯烃自由基双官能团化反应。
