Synthesis of hetero- and carbocycles by nucleophilic substitution at sp2 carbon
Synthesis of hetero- and carbocycles by nucleophilic substitution at sp2 carbon
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DOI：
10.1016/j.tet.2007.02.116
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发表时间：
2007-06-25
期刊：
影响因子：
2.1
通讯作者：
Narasaka, Koichi
中科院分区：
文献类型：
--
作者：
Miyauchi, Hironori;Chiba, Shunsuke;Narasaka, Koichi
具有醇、磺酰胺、活泼甲基和硫醇部分作为亲核剂的乙烯基卤化物，通过分子内的亲核取代在SP(2)碳中心环化成杂环和碳环。密度泛函理论计算表明，当卤代乙烯被氧、氮和碳亲核试剂取代时，环化反应通过S(N)2型取代(面内乙烯亲核取代，SNV sigma)进行。与硫亲核试剂的取代相反，通过SNVS和面外乙烯亲核取代(SNV Pi)两种途径进行。(C)2007爱思唯尔有限公司。保留所有权利。
Vinylic halides having alcohol, sulfonamide, active methine, and thiol moieties as nucleophiles cyclize to hetero- and carbocycles by intramolecular nucleophilic substitution at the sp(2) carbon centers. The density functional theory calculations suggest that the cyclization proceeds through S(N)2-type substitution (the in-plane vinylic nucleophilic substitution, SNV sigma), when vinyl halides are substituted with oxygen, nitrogen, and carbon nucleophiles. The substitution with sulfur nucleophiles, in contrast, proceeds through both routes of SNVs and out-of-plane vinylic nucleophilic substitution (SNV pi). (C) 2007 Elsevier Ltd. All rights reserved.