Sodium bicarbonate-catalyzed stereoselective isomerizations of electron-deficient propargylic alcohols to (Z)-enones
Sodium bicarbonate-catalyzed stereoselective isomerizations of electron-deficient propargylic alcohols to (Z)-enones
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DOI：
10.1021/jo0623944
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发表时间：
2007-03-02
影响因子：
3.6
通讯作者：
Koide, Kazunori
中科院分区：
文献类型：
--
作者：
Sonye, John P.;Koide, Kazunori
氧化还原异构化是一个非常重要的过程，因为它在产物中产生了两个新的官能团，其中一个是丙叉醇异构化为共轭烯酮。虽然已经用这种方法制备了E-烯酮，但不能获得Z-烯酮。我们以前曾报道过DABCO催化的电子缺乏丙叉醇的E-选择性异构化反应及其反应机理。基于这一机理，我们首次在碳酸氢钠催化下实现了缺电子丙叉醇的Z-选择性氧化还原异构化合成烯酮。
Redox isomerization is a synthetically important process because it creates two new functional groups in the product, among which is the isomerization of propargylic alcohols to conjugated enones. Although E-enones have been prepared by this approach, Z-enones could not be accessed. We previously reported DABCO-catalyzed E-selective isomerization of electron-deficient propargylic alcohols to enones and its mechanism. Based on this mechanism, we have now developed the first Z-selective redox isomerization of electron-deficient propargylic alcohol to enone using sodium bicarbonate as a catalyst.