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

Md Monarul Islam, Xing Feng, Chuan Zeng Wang, Shofiur Rahman, Abdullah Alodhayb, Paris E. Georghiou, Taisuke Matsumoto, Junji Tanaka, Carl Redshaw, Takehiko Yamato

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Abstract

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.

Original languageEnglish
Pages (from-to)1269-1274
Number of pages6
JournalChemistrySelect
Volume5
Issue number4
DOIs
Publication statusPublished - Jan 31 2020

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All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Monarul Islam, M., Feng, X., Wang, C. Z., Rahman, S., Alodhayb, A., Georghiou, P. E., ... Yamato, T. (2020). Studies on Lewis-Acid Induced Reactions of 8-Methoxy[2.2]metacyclophanes: A New Synthetic Route to Alkylated Pyrenes. ChemistrySelect, 5(4), 1269-1274. https://doi.org/10.1002/slct.201903048