Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cycloaddition of 3-Acyloxy 1,4-Enyne and Alkene

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• 作者：Xing-zhong Shu ; Casi M. Schienebeck ; Xiaoxun Li ; Xin Zhou ; Wangze Song ; Lianqing Chen ; Ilia A. Guzei ; Weiping Tang
• 刊名：Organic Letters
• 出版年：2015
• 出版时间：October 16, 2015
• 年：2015
• 卷：17
• 期：20
• 页码：5128-5131
• 全文大小：412K
• ISSN：1523-7052

文摘

The first rhodium-catalyzed intramolecular [5 + 2] cycloaddition of 3-acyloxy 1,4-enyne and alkene was developed. The cycloaddition is highly diastereoselective in most cases. Various cis-fused bicyclo[5.3.0]decadienes were prepared stereoselectively. The chirality in the propargylic ester starting materials could be transferred to the bicyclic products with high efficiency. Electron-deficient phosphine ligand greatly facilitated the cycloaddition. Up to three new stereogenic centers could be generated. The resulting diene in the products could be hydrolyzed to enones, which allowed the introduction of more functional groups to the seven-membered ring.