Cyclopentanone as a Cation-Stabilizing Electron-Pair Donor in the Calcium-Catalyzed Intermolecular Carbohydroxylation of Alkynes
Cyclopentanone as a Cation-Stabilizing Electron-Pair Donor in the Calcium-Catalyzed Intermolecular Carbohydroxylation of Alkynes
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DOI：
10.1021/acs.orglett.5b00312
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发表时间：
2015-03-20
期刊：
影响因子：
5.2
通讯作者：
Niggemann, Meike
中科院分区：
文献类型：
--
作者：
Stopka, Tobias;Niggemann, Meike
尽管它们已经在阳离子聚合中用作反应活性控制添加剂数十年，但刘易斯碱性电子对供体（艾德）化合物从未用于小分子转化中阳离子中间体的稳定。作为这样的艾德，环戊酮被证明与我们的钙基催化剂体系组合对于烯丙基和乙烯基阳离子的稳定是高效的。因此，首次实现了炔与烯丙醇和炔丙醇的无过渡金属的分子间碳羟基化反应。
Although they have been used as reactivity-controlling additives in cationic polymerizations for decades, Lewis basic electron pair donor (ED) compounds were never used for the stabilization of cationic intermediates in transformations of small molecules. As such an ED, cyclopentanone proved highly efficient for the stabilization of allyl and vinyl cations in combination with our calcium-based catalyst system. Therefore, the first general transition-metal-free intermolecular carbohydroxylation of alkynes with allyl and propargyl alcohols was realized.