School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou, 221116, P. R. China.
Chem Commun (Camb). 2019 Dec 5;55(98):14757-14760. doi: 10.1039/c9cc08762a.
A Lewis acid-catalyzed insertion of unsymmetrical alkynes into electron-deficient alkenes was developed for the first time, and used to produce 34 hitherto unreported pentacyclic benzo[5,6]chromeno[2,3-b]indoles with generally good yields and complete stereoselectivity. A Yb(OTf)3-catalyzed reaction between o-alkynylnaphthols and 3-methyleneindolin-2-ones proceeded efficiently, and provided a simple and convergent protocol for alkyne difunctionalization via oxidant-free C-C double bond breaking/rearrangement. Mechanistic details of this domino process were derived by conducting systematic theoretical calculations.
首次发展了一种路易斯酸催化的不对称炔烃插入缺电子烯烃的反应，用于合成 34 个迄今未见报道的具有良好收率和完全立体选择性的五环苯并[5,6]色烯并[2,3-b]吲哚。通过 Yb(OTf)3 催化邻炔基萘酚和 3-亚甲基吲哚啉-2-酮之间的反应，可以有效地进行，并且提供了一种通过无氧化剂 C-C 双键断裂/重排进行炔烃双官能化的简单而集中的方法。通过进行系统的理论计算，得出了该串联过程的详细机理。
