A computationally designed Rh(I)-catalyzed two-component [5+2+1] cycloaddition of ene-vinylcyclopropanes and CO for the synthesis of cyclooctenones.
A computationally designed Rh(I)-catalyzed two-component [5+2+1] cycloaddition of ene-vinylcyclopropanes and CO for the synthesis of cyclooctenones.
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DOI：
10.1021/ja072505w
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发表时间：
2007-07
影响因子：
15
通讯作者：
Yuanyuan Wang;Jingxin Wang;Jiachun Su;F. Huang;L. Jiao;Yong Liang;Dazhi Yang;Shiwei Zhang
中科院分区：
文献类型：
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作者：
Yuanyuan Wang;Jingxin Wang;Jiachun Su;F. Huang;L. Jiao;Yong Liang;Dazhi Yang;Shiwei Zhang
通过计算(密度泛函理论)和实验研究相结合的方法，设计并实验实现了一种新的[Rh(CO)2Cl2]2催化的双组分烯-乙烯基环丙烷与CO的[5+2+1]环加成反应，用于合成稠合双环辛烯酮。这种设计的关键是通过引入CO，将不受欢迎的(Sp3)C−Rh−C(Sp3)的还原消除转变为更容易的迁移还原消除(Sp3)C−Rh−CO−C(Sp3)。这些反应在具有各种系链类型和取代基的底物上以良好的产率进行，为构建双环环辛烯酮提供了一种灵活、方便、高效和立体可控的方法。
Through the combined use of computational (density functional theory) and experimental studies, a new [Rh(CO)2Cl]2 catalyzed two-component [5+2+1] cycloaddition of ene-vinylcyclopropanes and CO for the synthesis of fused bicyclic cyclooctenones has been designed and experimentally realized. The key point behind this design is to turn a disfavored reductive elimination of (sp3)C−Rh−C(sp3) to an easier migratory reductive elimination of (sp3)C−Rh−CO−C(sp3) by the introduction of CO. These reactions proceed in good yields for substrates with various tether types and substituents, providing a flexible, convenient, efficient, and stereocontrolled method for the construction of bicyclic cyclooctenones.