Synthesis, Structures and Lewis-Acid-Induced Isomerization of 8-Methoxy[2.2]metaparacyclophanes and a DFT Study

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

Research output: Contribution to journalArticle

Abstract

Methyl substituted 8-methoxy[2.2]MPCPs 8 a–b were obtained via thiacyclophane and its oxidized products. Lewis acid-catalyzed (AlCl 3 -MeNO 2 ) 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 1 H 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.

Original languageEnglish
Pages (from-to)3630-3635
Number of pages6
JournalChemistrySelect
Volume4
Issue number13
DOIs
Publication statusPublished - Apr 9 2019

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Lewis Acids
Cyclization
Isomerization
Benzene
Discrete Fourier transforms
Conformations
Nuclear magnetic resonance
Derivatives
X rays
Molecules
pyrene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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.

In: ChemistrySelect, Vol. 4, No. 13, 09.04.2019, p. 3630-3635.

Research output: Contribution to journalArticle

Islam, MM, Feng, X, Rahman, S, Georghiou, PE, Matsumoto, T, Tanaka, J, Alodhayb, A, Redshaw, C & Yamato, T 2019, 'Synthesis, Structures and Lewis-Acid-Induced Isomerization of 8-Methoxy[2.2]metaparacyclophanes and a DFT Study', ChemistrySelect, vol. 4, no. 13, pp. 3630-3635. https://doi.org/10.1002/slct.201900190
Islam, Md Monarul ; Feng, Xing ; Rahman, Shofiur ; Georghiou, Paris E. ; Matsumoto, Taisuke ; Tanaka, Junji ; Alodhayb, Abdullah ; Redshaw, Carl ; Yamato, Takehiko. / Synthesis, Structures and Lewis-Acid-Induced Isomerization of 8-Methoxy[2.2]metaparacyclophanes and a DFT Study. In: ChemistrySelect. 2019 ; Vol. 4, No. 13. pp. 3630-3635.
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