Synthesis, structures and Lewis‐Acid‐Induced isomerization of 8‐Methoxy[2.2]metaparacyclophanes and a DFT study

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

doi:10.1002/slct.201900190

Synthesis, structures and Lewis‐Acid‐Induced isomerization of 8‐Methoxy[2.2]metaparacyclophanes and a DFT study

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

Authors

Md. Monarul Islam

Xing Feng

Shofiur Rahman

Paris E. Georghiou

Taisuke Matsumoto

Junji Tanaka

Abdullah Alodhayb

Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry

Takehiko Yamato

Abstract

Methyl substituted 8‐methoxy[2.2]MPCPs 8 a–b were obtained via thiacyclophane and its oxidized products. Lewis acid‐catalyzed (AlCl3‐MeNO2) reactions of 5‐tert‐butyl‐8‐methoxy‐12,13,15,16‐tetramethyl[2.2]MPCP 8 b under various conditions led to transannular cyclization and isomerization reactions, affording the considerably less‐strained 5‐tert‐butyl‐8‐methoxy[2.2]MPCP 9, 5‐tert‐butyl‐8‐hydroxy‐14,16,17,18‐tetramethyl[2.2]metacyclophane 10 and pyrene derivatives 11 and 12. However,on prolonging the reaction time to 3 h for 8 b, the major product is 5‐tert‐butyl‐8‐hydroxy[2.2]MPCP 10. These reactions are strongly affected by the size and properties of the C‐8 substitutents as well as the methyl substitutents on the para‐linked benzene rings, which increase the strain in the molecules. The 1H NMR spectra and X‐ray crystallographic analysis of 8 b revealed that it adopts a syn‐conformation both in solution and in the solid state.

Citation

Islam, M. M., Feng, X., Rahman, S., Georghiou, P. E., Matsumoto, T., Tanaka, J., …Yamato, T. (2019). Synthesis, structures and Lewis‐Acid‐Induced isomerization of 8‐Methoxy[2.2]metaparacyclophanes and a DFT study. ChemistrySelect, 4(13), 3630-3635. https://doi.org/10.1002/slct.201900190

Journal Article Type	Article
Acceptance Date	Mar 14, 2019
Online Publication Date	Apr 1, 2019
Publication Date	Apr 9, 2019
Deposit Date	Apr 2, 2019
Publicly Available Date	Apr 2, 2020
Journal	ChemistrySelect
Electronic ISSN	2365-6549
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	4
Issue	13
Pages	3630-3635
DOI	https://doi.org/10.1002/slct.201900190
Keywords	Isomerization; Lewis acid; Metaparacyclophane; Strain; Transannular reaction; Trans-tert-butylation
Public URL	https://hull-repository.worktribe.com/output/1527613
Publisher URL	https://onlinelibrary.wiley.com/doi/full/10.1002/slct.201900190