Boyce Thompson Institute and Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA.
Org Lett. 2010 Sep 17;12(18):3986-9. doi: 10.1021/ol1015306.
We report a simple method for the highly regio- and stereoselective hydrolysis of α,β-epoxyalcohols. Treatment of enantiopure epoxyalcohols derived from Sharpless epoxidation with TBAF/H(2)O resulted in exclusive ring opening at the normally disfavored α-position, providing access to arabino- or lyxo-configured triols with full preservation of stereochemical purity. The method was applied in syntheses of 5-deoxy-l-arabinose (26) and a family of bicyclic acetals based on the insect pheromone hydroxybrevicomin (4).
我们报告了一种用于高度区域和立体选择性水解α,β-环氧化醇的简单方法。用 TBAF/H(2)O 处理源于 Sharpless 环氧化反应的对映纯环氧化醇，导致在通常不利的α-位进行了专一地开环，提供了对映体纯的阿拉伯糖或来苏糖构型的三醇，立体化学纯度得到完全保留。该方法应用于 5-脱氧-l-阿拉伯糖（26）和一系列基于昆虫信息素羟基保幼激素（4）的双环缩醛的合成中。
