Lewis Acid-Activated Reactions of Silyl Ketenes for the Preparation of α-Silyl Carbonyl Compounds
Lewis Acid-Activated Reactions of Silyl Ketenes for the Preparation of α-Silyl Carbonyl Compounds
复制标题
路易斯酸活化硅烷烯酮反应制备α-硅烷基羰基化合物
DOI：
10.1021/acs.joc.9b01859
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Pentzer, Emily B.
中科院分区：
文献类型：
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作者：
Mitchell, Sarah M.;Xiang, Yuanhui;Matthews, Rachael;Amburgey, Alexis M.;Pentzer, Emily B.
与不稳定的烷基和芳基乙烯酮相比，甲硅烷基取代的乙烯酮由于其稳定性和易于储存而成为有吸引力的分子结构单元。为了更好地了解甲硅烷基乙烯酮的反应性以及它们在制备高功能化小分子中的用途，研究了甲硅烷基乙烯酮与不同亲核试剂的反应。将醇、胺或硫醇亲核试剂加成到甲硅烷基烯酮的中心碳上，然后进行质子转移，分别得到α-甲硅烷基酯、酰胺或硫代酯。路易斯酸的催化量大大提高了反应速率，并评估了亲核试剂、路易斯酸和甲硅烷基取代基的影响。这些反应产生的小分子让我们深入了解甲硅烷基乙烯酮作为复杂分子结构的构建模块的用途。
Silyl-substituted ketenes are attractive molecular building blocks due to their stability and ease of storage, as opposed to unstable alkyl and aryl ketenes. To better understand the reactivity of silyl ketenes and, in turn, their use in the preparation of highly functionalized small molecules, the reaction of silyl ketenes with different nucleophiles was studied. The addition of alcohol, amine, or thiol nucleophiles to the central carbon of silyl ketene, followed by proton transfer afforded α-silyl ester, amide, or thio-ester, respectively. Catalytic amounts of Lewis acid greatly increase the rate of the reaction, and the impact of nucleophile, Lewis acid, and silyl substituent are evaluated. The small molecules produced from these reactions give insight into the use of silyl ketenes as building blocks for complex molecular structures.