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

doi:10.1002/slct.201903048

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

Authors

Md Monarul Islam

Xing Feng

Chuan Zeng Wang

Shofiur Rahman

Abdullah Alodhayb

Paris E. Georghiou

Taisuke Matsumoto

Junji Tanaka

Emeritus Professor Carl Redshaw C.Redshaw@hull.ac.uk
Emeritus Professor

Takehiko Yamato

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.

Citation

Monarul Islam, M., Feng, X., Wang, C. Z., Rahman, S., Alodhayb, A., Georghiou, P. E., Matsumoto, T., Tanaka, J., Redshaw, C., & 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

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
DOI	https://doi.org/10.1002/slct.201903048
Keywords	DFT computations; Lewis acids; Metacyclophanes; Ring strain; Syn-anti conformers; Transannular cyclizations; Trans-tert-butylation
Public URL	https://hull-repository.worktribe.com/output/3621758
Publisher URL	https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/slct.201903048