Wehming Kathrin, Schubert Moritz, Schnakenburg Gregor, Waldvogel Siegfried R
Mainz University, Institute for Organic Chemistry, Duesbergweg 10-14, 55128 Mainz (Germany), Fax: (+49) 6131 3926777.
Chemistry. 2014 Sep 22;20(39):12463-9. doi: 10.1002/chem.201403442. Epub 2014 Jul 17.
The oxidative cyclization reaction of 2-aryl cinnamates and derivatives thereof can be easily performed with MoCl5 as the oxidant. This powerful reagent allows oxidative coupling reactions for which other reagents fail. The best results are obtained when the 2-phenyl substituent of the cinnamate is equipped with two methoxy groups. Even iodo moieties in the bay region of phenanthrene are tolerated under the reaction conditions. If naphthalene moieties are involved, a rearrangement of the skeleton occurs, providing an elegant route to highly functionalized angular arenes. The cyclization is demonstrated for 15 example substrates with isolated yields of up to 99 % for the phenanthrene derivative. The broad scope of the reaction underlines the usefulness of MoCl5 and MoCl5 /TiCl4 in the oxidative coupling reaction.
以五氯化钼为氧化剂，2-芳基肉桂酸酯及其衍生物的氧化环化反应能够轻松实现。这种强大的试剂可用于其他试剂无法实现的氧化偶联反应。当肉桂酸酯的2-苯基取代基带有两个甲氧基时，能获得最佳结果。在该反应条件下，菲的湾区甚至碘部分也能耐受。若涉及萘部分，则会发生骨架重排，为高度官能化的角状芳烃提供了一条优雅的合成路线。以15个示例底物展示了环化反应，菲衍生物的分离产率高达99%。该反应的广泛适用范围突显了五氯化钼和五氯化钼/四氯化钛在氧化偶联反应中的实用性。
