MoV Reagents in Organic Synthesis
MoV Reagents in Organic Synthesis
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DOI：
10.1002/ejoc.201600025
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发表时间：
2016-03
影响因子：
2.8
通讯作者：
M. Schubert;S. Waldvogel
中科院分区：
文献类型：
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作者：
M. Schubert;S. Waldvogel
综述了MoV试剂，特别是MoCl5在有机合成中的应用。芳香族底物的氧化处理是最常见的应用。这些试剂的独特性质是由于它们的高氧化能力与精致的路易斯酸性质相结合。在几个例子中，MoV试剂优于其他常见的氧化偶联试剂。通过分子间和分子内氧化偶联形成的C-C键可以选择性地形成五至八元环体系。对MoV试剂和芳香族底物反应过程的机理研究表明，自由基阳离子最初形成，进入氧化偶联状态。机制研究表明，scholl型转换是不可能的。然而，产品的过度氧化似乎是选择性转化的基本原理。还原发生在加工过程中，通过存在的低价钼盐的作用。这打开了氧化多米诺骨牌序列的途径。MoCl5已被用于几种天然产物或其类似物合成的关键步骤。此外，MoCl5可用于氯化反应和通过模板形成的立体选择性异构化反应，也可作为炔三聚体化的前体。
The use of MoV reagents, and in particular MoCl5, in organic synthesis is surveyed. The oxidative treatment of aromatic substrates is the most common application. The unique properties of these reagents are due to their high oxidative power combined with exquisite Lewis acid properties. In several examples MoV reagents outperform other common oxidative coupling reagents. C–C bond formation through inter- and intramolecular oxidative coupling can lead to selective formation of five- to eight-membered ring systems. Mechanistic investigations of the courses of reactions involving MoV reagents and aromatic substrates indicate that radical cations are initially formed, entering the oxidative coupling scenery. Mechanistic studies reveal that Scholl-type conversion is unlikely. However, over-oxidation of the product seems to be the rationale for the selective conversion. Reduction occurs during workup, through the action of the lower-valency molybdenum salts present. This opens up the pathway to oxidative domino sequences. MoCl5 has already been used in the key steps of the syntheses of several natural products or their analogues. In addition, MoCl5 can serve in chlorination reactions and in stereoselective isomerization by template formation, and also as a precursor for alkyne trimerization.