Synthesis of hetero- and carbocycles by nucleophilic substitution at sp carbon |
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Authors: | Hironori Miyauchi Koji Fukamizu Koichi Narasaka |
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Institution: | a Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan b College of Education, University of the Ryukyus, 1 Senbaru, Nisihara-cho, Okinawa 903-0213, Japan |
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Abstract: | 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 SN2-type substitution (the in-plane vinylic nucleophilic substitution, SNVσ), when vinyl halides are substituted with oxygen, nitrogen, and carbon nucleophiles. The substitution with sulfur nucleophiles, in contrast, proceeds through both routes of SNVσ and out-of-plane vinylic nucleophilic substitution (SNVπ). |
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Keywords: | Haloalkenes Nucleophilic substitution Cyclization Density functional theory |
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