Skip to main content

Research Repository

Advanced Search

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

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


Md Monarul Islam

Xing Feng

Chuan Zeng Wang

Shofiur Rahman

Abdullah Alodhayb

Paris E. Georghiou

Taisuke Matsumoto

Junji Tanaka

Profile Image

Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry

Takehiko Yamato


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.


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.

Journal Article Type Article
Acceptance Date Jan 8, 2020
Online Publication Date Jan 24, 2020
Publication Date Jan 31, 2020
Deposit Date Dec 8, 2020
Publicly Available Date Jan 25, 2021
Journal ChemistrySelect
Electronic ISSN 2365-6549
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 5
Issue 4
Pages 1269-1274
Keywords DFT computations; Lewis acids; Metacyclophanes; Ring strain; Syn-anti conformers; Transannular cyclizations; Trans-tert-butylation
Public URL
Publisher URL


Article (1.9 Mb)

Copyright Statement
©2020 The authors. All rights reserved. No part of this publication may be reproduced without the written permission of the copyright holder

You might also like

Downloadable Citations