Palladium-catalyzed cross-coupling reactions of silanolates: A paradigm shift in silicon-based cross-coupling reactions
Palladium-catalyzed cross-coupling reactions of silanolates: A paradigm shift in silicon-based cross-coupling reactions
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DOI：
10.1002/chem.200600034
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发表时间：
2006-06-23
影响因子：
4.3
通讯作者：
Baird, John D.
中科院分区：
文献类型：
--
作者：
Denmark, Scott. E.;Baird, John D.
本文叙述了钯催化有机硅醇共轭碱交叉偶联反应的概念发展、原理实验证明和最新进展。这一发现导致了这一过程的设计和改进，它代表了一个经典的例子，说明机械研究如何为发明新反应提供肥沃的土壤。基于一个工作假设（最终被证明是不正确的）和希望在没有氟活化的情况下实现硅基交叉偶联的愿望，已经开发了一种温和实用的钯催化的烯基、芳基和杂基硅烷酸酯的交叉偶联。描述了该技术的机理基础、方法扩展以及在复杂分子合成中的成功应用。
This paper chronicles the conceptual development, proof of principle experiments, and recent advances in the palladium-catalyzed cross-coupling reactions of the conjugate bases of organosilanols. The discovery that led to the design and refinement of this process represents a classical illustration of how mechanistic studies can provide a fertile ground for the invention of new reactions. On the basis of a working hypothesis (which ultimately proved to be incorrect) and the desire to effect silicon-based cross-coupling without the agency of fluoride activation, a mild and practical palladium-catalyzed cross-coupling of alkenyl-, aryl-, and heteroar-yl silanolates has been developed. The mechanistic underpinninas, methodological extensions, and the successful applications of this technology to the synthesis of complex molecules are described.