Palladium(II)-catalysed rearrangement reactions
Palladium(II)-catalysed rearrangement reactions
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DOI：
10.2174/138527206777435490
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发表时间：
2006-06-01
影响因子：
2.6
通讯作者：
Sutherland, Andrew
中科院分区：
文献类型：
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作者：
Fanning, Kate N.;Jamieson, Andrew G.;Sutherland, Andrew
以立体化学的方式合成新的碳-碳和碳-杂原子键仍然是现代合成方法学中的一个挑战。可以进行上述转化的一类重要的反应是[3，3]-Sigmatrotic重排。这些重排传统上是在高温下热进行的。然而，Pd(II)可以在常温下加速这些反应的发现，使得这些反应在合成生物活性和药用重要分子方面得到了更广泛的应用。本文综述了钯(II)催化在有机化学中最常用的三种重排反应的应用，即Cope重排、Claisen重排和Aza-Claisen重排。重点讨论了这些反应的催化机理、立体化学产物和合成应用。
The synthesis of new carbon-carbon and carbon-heteroatom bonds in a stereochemically well defined manner still presents a challenge in modern synthetic methodology. An important class of reactions, which can carry out the aforementioned transformations, are the [3,3]-sigmatropic rearrangements. These rearrangements have traditionally been carried out thermally at high temperatures. However, the discovery that these transformations can be accelerated by Pd(II) at ambient temperature has led to more widespread use of these reactions for the synthesis of biologically active and pharmaceutically important molecules.This review presents an overview of the use of palladium(II) catalysis for the acceleration of three of the most commonly used rearrangements in organic chemistry, namely, the Cope, Claisen and aza-Claisen rearrangements. In particular, the mechanism of catalysis, stereochemical outcome and synthetic application of these reactions will be discussed.