Stereoselective Synthesis of δ-Lactones from 5-Oxoalkanals via One-Pot Sequential Acetalization, Tishchenko Reaction, and Lactonization by Cooperative Catalysis of Samarium Ion and Mercaptan
作者:Jue-Liang Hsu、Jim-Min Fang
DOI:10.1021/jo016058t
日期:2001.12.1
sequence of acetalization, Tishchenko reaction and lactonization. The deliberative use of mercaptan, by comparison with alcohol, is advantageous to facilitate the catalytic cycle. The reaction mechanism and stereochemistry are proposed and supported by some experimental evidence. Such samarium ion/mercaptan cocatalyzed reactions show the feature of remote control, which is applicable to the asymmetric synthesis
通过sa离子和硫醇的协同催化,一系列5-氧代烷醛以有效和立体选择性的方式转化为(取代的)δ-内酯。这一一锅法包括一系列缩醛化,Tishchenko反应和内酯化。与醇相比,有意使用硫醇有利于促进催化循环。提出了反应机理和立体化学,并得到了一些实验证据的支持。sa离子/硫醇共催化反应显示出远程控制的特征,适用于旋光性δ-内酯的不对称合成。这项研究还证明了两种昆虫信息素(2S,5R)-2-甲基己内酯和(R)-十六烷内酯的合成,