Synthetic approach towards cuparene-type sesquiterpenes via highly regioselective epoxide opening under acid catalysis
作者:Camila B. Nascimento、Leandro A. Avelar、Danilo C. Arantes、Noêmia K. Ishikawa、Fernando Macedo
DOI:10.1007/s00706-018-2199-6
日期:2018.10
AbstractObtaining cuparene-type sesquiterpenes is a significant synthetic challenge mainly because of the construction of the sterically hindered quaternary centres. We report herein the successful construction of such quaternary moiety by a highly regioselective opening of (+/−)-2,5-dimethoxy-4-methyl-α-methylstyrene oxide by the acetone silyl enol ether catalysed by Lewis acid. Additionally, an efficient
摘要获得铜烯型倍半萜烯是一项重大的合成挑战,这主要是由于立体位阻四元中心的构建。我们在本文中报道了通过路易斯酸催化的丙酮甲硅烷基烯醇醚的(+/-)-2,5-二甲氧基-4-甲基-α-甲基苯乙烯氧化物的高度区域选择性开放来成功构建此类季基部分。另外,通过对二环氧乙烷促进的环氧化方案的修饰,实现了高度活化的2,5-二甲氧基-4-甲基-α-苯乙烯的有效环氧化。对这两个关键步骤的密集优化使所需支链高醛缩醛加合物的合成成为了针对烯醇单蛋白的短合成替代品的关键中间体。 图形概要