Bronsted Acid Catalyzed Synthesis of Functionalized 1,4-and 1,6-Dicarbonyl Monosilyl Enol Ethers under Operationally Practical Conditions
Bronsted Acid Catalyzed Synthesis of Functionalized 1,4-and 1,6-Dicarbonyl Monosilyl Enol Ethers under Operationally Practical Conditions
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DOI：
10.1021/acs.joc.7b01687
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发表时间：
2017-10-06
影响因子：
3.6
通讯作者：
Kartika, Rendy
中科院分区：
文献类型：
--
作者：
Malone, Joshua A.;Van Houten, Joshua P.;Kartika, Rendy
在这里，我们报告了一种改进的方法，通过电离α‘-羟基硅烯醇醚生成不对称的硅氧基烯丙基阳离子，然后被TBS硅烯醇酸盐捕获，从而简明地合成功能化的1，4-和1，6-二羰基衍生的单硅醇醚。在室温下，以三氟化吡啶为催化剂，在乙腈中有效地进行了这些转化。我们的新反应条件在操作上更实用，并扩大了各种1，4-和1，6-二羰基的可及性，包括二酮、酮酯和酮硫酸酯官能团。
Herein, we report an improved protocol for the concise synthesis of functionalized 1,4- and 1,6-dicarbonyl-derived monosilyl enol ethers via ionization of alpha'-hydroxy silyl enol ethers to generate unsymmetrical silyloxyallyl cations that were subsequently captured by TBS silyl enolates. These transformations were efficiently performed in acetonitrile at room temperature by employing pyridinium triflate as a catalyst. Our new reaction conditions are operationally more practical and broaden the accessibility of various 1,4- and 1,6-dicarbonyl groups, which include diketone, ketoester, and ketothioester functionalities.