Chen Wenkun, Jiang Jijun, Wang Jun
School of Chemistry, Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, Sun Yat-Sen University, 510006, Guangzhou, P. R. China.
Angew Chem Int Ed Engl. 2024 Feb 5;63(6):e202316741. doi: 10.1002/anie.202316741. Epub 2023 Dec 29.
A versatile and readily available chiral amide directing group has been developed for the ruthenium(II)-catalyzed asymmetric C-H activation. Asymmetric C-H activation of the related chiral benzamides with various olefins, aldehydes and propargylic alcohols has been accomplished with high stereoselectivities, affording a series of chiral products including 3,4-dihydroisocoumarins (up to 96 % ee), isocoumarins (up to 92 % ee), phthalides (up to 99 % ee), chiral bicyclo[2.2.1]heptanes (>20 : 1 dr), 4-alkylidene-3,4-dihydroisocoumarins (up to 97 % ee) and allenes (>20 : 1 dr). Importantly, our methodologies enabled concise syntheses of many biologically active compounds and natural products (e.g., Montroumarin, Cyclosporone E, Cyclosporone Q, Concentricolide, Chuangxinol, and Eleutherol).
一种通用且易于获得的手性酰胺导向基团已被开发用于钌（II）催化的不对称C-H活化反应。通过与各种烯烃、醛和炔丙醇进行相关手性苯甲酰胺的不对称C-H活化反应，已实现了高立体选择性，得到了一系列手性产物，包括3,4-二氢异香豆素（对映体过量高达96%）、异香豆素（对映体过量高达92%）、苯酞（对映体过量高达99%）、手性双环[2.2.1]庚烷（非对映体比例>20:1）、4-亚烷基-3,4-二氢异香豆素（对映体过量高达97%）和丙二烯（非对映体比例>20:1）。重要的是，我们的方法能够简洁地合成许多生物活性化合物和天然产物（例如，蒙曲马林、环孢菌素E、环孢菌素Q、同心内酯、创新醇和刺五加醇）。
