手性α-烯丙基苯甲醇的立体选择性合成研究

Stereoselective synthesis of chiral α-allylbenzyl alcohol

为研究手性烯丙基硼酒石酸衍生物在不对称烯丙基化反应中的立体选择性作用,将光学纯酒石酸经酯化或酰胺化反应后与烯丙基硼烷作用生成手性烯丙基硼酒石酸衍生物,与苯甲醛反应后用碱液淬灭即可得手性α-烯丙基苯甲醇。通过比较酒石酸苯甲酯和酒石酰苯胺等手性配体反应后得到的最终产物的光学收率,可知由酒石酰苄胺控制的产物光学收率更高;同时,用密度泛函理论(DFT)的B3LYP/6-31G(d,p)方法在Gaussian 03软件上对该类型的反应进行了模拟计算,得出的计算结果也是由酒石酰苄胺控制的产物光学收率更高,与计算结果相吻合.

In order toget a-allylbenzyl alcohol with high entiomeric excess and study the effect of stereoselectivity of allyboronate tartrate derivates in the synthesis of α-allylbenzyl alcohol, optically pure tartrate was esterified or amideted to get optically pure allylboronate tartrate derivates, and the allylboronate tartrate derivates were used to react with benzaldehyde and then quenched with alkaline solution to get α-allylbenzyl alcohol. By comparing the entiomeric excess of the reactions it was concluded that the entiomeric excess of α-allylbenzyl alcohol controlled by benzylamine tartrate was higher than that of tartrate esters, and the experimental results were in agreement with the calculated result based on density functional theory （DFT） at B3LYP/6-31 G（d,p） on Gaussian 03. The reactions are allylboronate tartrate derivates such as phenylamine tartrate and benzylamine tartrate reacted with benzaldehyde.