Cobalt-Catalyzed Enantioselective C–H Annulation of Benzylamines with Alkynes: Application to the Modular and Asymmetric Syntheses of Bioactive Molecules
作者:Yong-Jie Wu、Jia-Hao Chen、Ming-Ya Teng、Xiang Li、Tian-Yu Jiang、Fan-Rui Huang、Qi-Jun Yao、Bing-Feng Shi
DOI:10.1021/jacs.3c10714
日期:——
enantioselective C–H functionalization strategy has revolutionized the logic of natural product synthesis. However, previous applications have heavily relied on the use of noble metal catalysts such as rhodium and palladium. Herein, we report the efficient synthesis of C1-chiral 1,2-dihydroisoquinolines (DHIQs) via enantioselective C–H/N–H annulation of picolinamides with alkynes catalyzed by a more sustainable and
过渡金属催化的对映选择性C-H官能化策略彻底改变了天然产物合成的逻辑。然而,以前的应用严重依赖于贵金属催化剂的使用,例如铑和钯。在此,我们报道了在更可持续且更便宜的3d金属催化剂乙酸钴(II)的催化下,通过吡啶甲酰胺与炔烃的对映选择性C-H/N-H环化,有效合成了C 1 -手性1,2-二氢异喹啉(DHIQ)四水合物。以良好的收率和优异的对映选择性(高达 98% 收率和 >99% ee)获得了各种对映体富集的 DHIQ。该方法的稳健性和合成潜力通过几种四氢异喹啉生物碱的模块化和不对称合成得到了证明,这些生物碱包括( S )-降劳丹苷、( S )-劳丹苷、( S )-木洛匹宁、( S )-sebiferine和( S ) -cryptostyline II,以及 (+)-solifenacin、FR115427 和 (+)-NPS R-568 关键中间体的不对称合成。