Studies on Lewis‐Acid Induced Reactions of 8‐Methoxy[2.2]metacyclophanes: A New Synthetic Route to Alkylated Pyrenes,ChemistrySelect

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Studies on Lewis‐Acid Induced Reactions of 8‐Methoxy[2.2]metacyclophanes: A New Synthetic Route to Alkylated Pyrenes
ChemistrySelect ( IF 1.9 ) Pub Date : 2020-01-24 , DOI: 10.1002/slct.201903048
Md. Monarul Islam _{1,

2,

3} , Xing Feng ₃ , Chuan‐Zeng Wang ₂ , Shofiur Rahman _{4,

5} , Abdullah Alodhayb _{4,

6} , Paris E. Georghiou ₅ , Taisuke Matsumoto ₇ , Junji Tanaka ₇ , Carl Redshaw ₈ , Takehiko Yamato _{2,

9}

Affiliation

Chemical Research Division Bangladesh Council of Scientific and Industrial Research (BCSIR) Dhanmondi, Dhaka 1205 Bangladesh
Department of Applied Chemistry, Faculty of Science and EngineeringSaga University Honjo-machi 1 Saga 840-8502 Japan
Guangdong Provential Key Laboratory ofFunctionalSoft Condensed Matter,School of Materials andEnergyGuangdong University of Technology Guangzhou 510006 P. R. China
Aramco Laboratory for Applied Sensing Research, King Abdullah Institute for NanotechnologyKing Saudi University Riyadh 11451, Saudi Arabia.
Department of ChemistryMemorial University of Newfoundland St. John's, Newfoundland and Labrador A1B 3X7 Canada
Research Chair for Tribology, Surface, and Interface Sciences, Department of Physics and AstronomyCollege of Science, King Saudi University Riyadh 11451 Saudi Arabia
Institute of Materials Chemistry and EngineeringKyushu University 6-1, Kasugakoen Kasuga 816-8580 Japan
Department of Chemistry & BiochemistryThe University of Hull Cottingham Road Hull, Yorkshire HU6 7RX UK
Loker Hydrocarbon Research InstituteUniversity of Southern California Los Angeles, CA 90089-1661 USA

Anti‐8‐methoxy[2.2]metacyclophanes (MCPs) 5 a–b were obtained via pyrolysis of the corresponding syn‐thiatetraoxide cyclophanes 4 a–b. Coupling reactions of 4‐tert‐butyl‐1‐methoxy‐2,6‐bis(mercaptomethyl)benzenes 1 a–b and 1,5‐bis(chloro‐methyl)‐2,4‐dimethylbenzene 2 under high dilution conditions afforded only the syn‐conformers of 9‐methoxy‐2,11‐dithia[3.3]metacyclophanes 3 a–b, which with m‐CPBA formed the corresponding syn‐tetraoxides 4 a–b. Lewis acid (TICl₄/AlCl₃‐MeNO₂) or iodine‐catalyzed reactions of 5 b under various conditions led to transannular cyclization to afford tetrahydropyrene 6 b and pyrene derivative 7 b and/or de‐tert‐butylated 6 a. Iodine‐catalyzed reaction of 5 a afforded tetrahydropyrene 6 a. These findings suggest the potential for a new route to alkylated pyrenes via strained and alkylated metacyclophanes. Density functional theory (DFT) studies were carried out to investigate the conformational characteristics of 3–5.

中文翻译：

刘易斯酸诱导的8-甲氧基[2.2]亚甲基环烷反应的研究：一种合成烷基化比利牛斯的新途径

反-8-甲氧基[2.2] metacyclophanes（MCP）的5 一- b分别经由相应的热解获得的顺式-thiatetraoxide环芳4 一- b。偶合4-的反应叔丁基-1-甲氧基-2,6-双（巯基甲基）苯1 一- b和1,5-双（氯甲基）-2,4-二甲基苯2高度稀释的条件下仅得到所述顺式-9-甲氧基-2,11-二硫杂的-conformers [3.3] metacyclophanes 3 一- b，其与米-CPBA形成的相应顺式-四氧化物4 a – b。路易斯酸（的TiCl ₄ /的AlCl ₃ -MeNO ₂）或碘催化的反应5 b导致跨环环化在各种条件下，得到四氢芘6 b和芘衍生物7 b和/或脱叔-butylated 6 一个。碘催化5 a生成四氢py 6 a。这些发现暗示了通过应变和烷基化的亚甲基环烷烃通往烷基化pyr的新途径的潜力。进行了密度泛函理论（DFT）研究以研究3–5的构象特征。

更新日期：2020-01-24

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