三环羧酸酯的α－羟基化反应研究

Studies on α-Hydroxylation of Ticyclic Carboxylates

三环羧酸酯（Ⅱ）在强碱ＬＤＡ作用下经过烯醇中间体，由空气氧对其进行氧化，在羰基α－位引入一个过氧键，尔后用亚硫酸钠还原得到三环羟基羧酸酯（Ⅲ）。用量子化学ＡＭ１计算结果分析了Ⅲｂ分子中形成分子内氢键的原因及其与Ⅲａ和Ⅲｃ之间的区别。

Tricyclic carboxylates (Ⅱ) were enolated by hindered base lithium diisopropylamide(LDA),peroxide bond was introduced into α-position of carbonyl group by the oxidation with molecularoxygen. And then the peruxide intermediates were treated with aqueous sodium sulfite, the tricyclic hydrox-yearboxylates(Ⅲ)were obtained,With the results of AM1 calculation,we have discussed the reason forthe formation of intramolecular hydrogen bond in Ⅲb,and the differences between ⅢbandⅢa,Ⅲc were also studied.