Departamento de Química Orgánica, Instituto Politécnico Nacional, Escuela Nacional de Ciencias Biológicas, Prolongación de Carpio y Plan de Ayala s/n, Col. Santo Tomas., Alc. Miguel Hidalgo, Ciudad de México 11340, Mexico.
Molecules. 2022 Apr 28;27(9):2810. doi: 10.3390/molecules27092810.
A representative number of decalin and hydrindane derivatives - were prepared in 11-91% yield by means of a cascade reaction of cyclohexanone/cyclopentanone enolates and methyl acrylate through a Michael-Michael ring closure (MIMIRC) process. The relative stereochemistry of the four stereogenic centers formed in all products was determined by analyzing the vicinal coupling constants from the H NMR and X-ray crystallography. Such a stereochemical outcome was corroborated by conformational analysis supported by DFT calculations and simulating the H NMR spectra of representative products. All products showed the same relative stereochemistry at C-1 and C-8a, while at C-3 and bridgehead carbon C-4a, configurational changes were observed. The present results provide some insights about the scope and limitations of the triple cascade reaction between cycloalkanone enolates with methyl acrylate. This synthetic protocol is still a simple and very practical alternative to generate decalin and hydrindane derivatives with great structural diversity.
通过环己酮/环戊酮烯醇盐和甲基丙烯酸甲酯的迈克尔-迈克尔环闭合（MIMIRC）反应级联反应，以 11-91%的产率制备了相当数量的十氢化萘和四氢萘衍生物。通过分析从 1H NMR 和 X 射线晶体学获得的相邻偶合常数来确定所有产物中形成的四个立体中心的相对立体化学。这种立体化学结果得到了通过 DFT 计算和模拟代表产物的 1H NMR 谱来支持的构象分析的证实。所有产物在 C-1 和 C-8a 处均具有相同的相对立体化学，而在 C-3 和桥头碳 C-4a 处观察到构象变化。目前的结果提供了一些关于环己烷酮烯醇盐与甲基丙烯酸甲酯之间的三重级联反应的范围和限制的见解。该合成方案仍然是生成具有高度结构多样性的十氢化萘和四氢萘衍生物的简单而非常实用的替代方法。
