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Abstract：
We report a range of highly regioselective openings of [1.1.1]propellane with various allylic zinc halides, as well as zinc enolates of ketones, esters and nitriles. The resulting zincated bicyclopentanes (BCPs) were trapped with a range of electrophiles including acyl chlorides, sulfonothioates, hydroxylamino benzoates, tosyl cyanide as well as aryl and allyl halides, generating highly functionalized BCP-derivatives. The unusually high regioselectivity of these reactions has been rationalized using DFT calculations. A bioisostere of the synthetic opioid pethidine was prepared in 95 % yield in one step using this method.
摘要：
我们报告了一系列具有各种烯丙基卤化锌的[1.1.1]推进剂的高度区域选择性开口，以及酮的烯醇酸锌，酯和腈。所得的锌化双环戊烷（BCP）被一系列的亲电体捕获，包括酰氯，硫代磺酸酯,羟基氨基苯甲酸酯，甲苯磺酰基氰化物以及芳基和烯丙基卤化物，生成高度官能化的BCP衍生物。这些反应的异常高的区域选择性已使用DFT计算合理化。使用该方法一步以95％的产率制备合成阿片类哌替啶的生物等排物。
