Intramolecular Photocycloaddition Reactions of Arylcyclopropane Tethered 1-Cyanonaphthalenes.
Intramolecular Photocycloaddition Reactions of Arylcyclopropane Tethered 1-Cyanonaphthalenes.
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DOI：
10.1021/acs.joc.6b01721
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发表时间：
2016-08
期刊：
影响因子：
--
通讯作者：
H. Maeda;S. Matsuda;K. Mizuno
中科院分区：
文献类型：
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作者：
H. Maeda;S. Matsuda;K. Mizuno
研究了含芳环丙烷侧链的1-氰萘分子内光环加成反应。在这个家族的成员中，芳基环丙烷部分在1-氰萘环的2位键合的光反应产生头对头和头对尾的1,2-[3+2]光环加合物。另一方面，该家族中含有芳基环丙烷侧链的物质与氰芳烃环的4位相连，通过光反应形成[4+3]光环加合物和新的九元环产物，这些产物是通过光化学诱导最初形成的分子内[3+2]环加合物的10π控制环开口而产生的。溶剂效应和荧光研究的结果以及相应的分子间光反应的结果表明，光环加合物主要是通过分子内异构体机制形成的，当CH3CN为溶剂时，通过两性离子双自由基形成的光诱导分子内电子转移途径可能是该过程的部分原因。
Intramolecular photocycloaddition reactions of 1-cyanonaphthalenes bearing an arylcyclopropane containing side chain were investigated. Photoreactions of members of this family in which the arylcyclopropane moiety is bonded at the 2-position of the 1-cyanonaphthalene ring produce head-to-head and head-to-tail 1,2-[3+2] photocycloadducts. On the other hand, substances in this family containing an arylcyclopropane side chain linked to the 4-position of the cyanoarene ring undergo photoreactions to form [4+3] photocycloadducts along with novel nine-membered ring products, which are produced by photochemically induced 10π conrotatory ring opening of the initially formed intramolecular [3+2] cycloadducts. The results of solvent effects and fluorescence investigations along with those focusing on corresponding intermolecular photoreactions demonstrate that the photocycloadducts are formed predominantly through an intramolecular exciplex mechanism and that a photoinduced intramolecular electron transfer pathway via zwitterionic biradicals might be partly responsible for the process when CH3CN is the solvent.