Synthesis of hetero- and carbocycles by nucleophilic substitution at sp² carbon

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• 作者：Hironori Miyauchi ; Shunsuke Chiba ; Koji Fukamizu ; Kaori Ando ; Koichi Narasaka
• 关键词：Haloalkenes ; Nucleophilic substitution ; Cyclization ; Density functional theory
• 刊名：Tetrahedron
• 出版年：2007
• 出版时间：25 June 2007
• 年：2007
• 卷：63
• 期：26
• 页码：5940-5953
• 全文大小：1557 K

文摘

Vinylic halides having alcohol, sulfonamide, active methine, and thiol moieties as nucleophiles cyclize to hetero- and carbocycles by intramolecular nucleophilic substitution at the sp² carbon centers. The density functional theory calculations suggest that the cyclization proceeds through S_N2-type substitution (the in-plane vinylic nucleophilic substitution, S_NVσ), when vinyl halides are substituted with oxygen, nitrogen, and carbon nucleophiles. The substitution with sulfur nucleophiles, in contrast, proceeds through both routes of S_NVσ and out-of-plane vinylic nucleophilic substitution (S_NVπ).