Selective Intermolecular Oxidative Cross-Coupling of Enolates
Selective Intermolecular Oxidative Cross-Coupling of Enolates
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DOI：
10.1021/jacs.5b05058
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发表时间：
2015-08-19
影响因子：
15
通讯作者：
Hirao, Toshikazu
中科院分区：
文献类型：
--
作者：
Amaya, Toru;Maegawa, Yusuke;Hirao, Toshikazu
烯醇酸酯的选择性分子间氧化交叉偶联反应是碳负离子之间的成键反应，尽管它在直接合成不对称1，4-二酮方面具有潜在的应用价值，但仍是一个尚未解决的问题。主要的困难来自不可避免的同质耦合。我们的策略依赖于一种烯醇的选择性单电子氧化来提供亲电的羰基α-自由基物种，然后用另一种烯醇捕获。本研究证实了选择性氧钒(V)诱导的硼和硅烯醇酸盐之间的交叉偶联。
Selective intermolecular oxidative cross-coupling of enolates, which is a bond-forming reaction between carbanion equivalents, remains as an unsolved issue despite its potential utility for the direct synthesis of unsymmetrical 1,4-diones. The main difficulty derives from the unavoidable homo-coupling. Our strategy depends on the selective one-electron oxidation of one enolate to afford an electrophilic carbonyl alpha-radical species, followed by trapping with another enolate. The present study demonstrates the selective oxovanadium(V)-induced cross-coupling between boron and silyl enolates.