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Synthesis, Conformational Properties and DFT Computational Studies of Polymethyl-Substituted [3.3]Metacyclophanes

Islam, Md Monarul; Akther, Thamina; Rahman, Shofiur; Georghiou, Paris E.; Matsumoto, Taisuke; Tanaka, Junji; Redshaw, Carl; Yamato, Takehiko


Md Monarul Islam

Thamina Akther

Shofiur Rahman

Paris E. Georghiou

Taisuke Matsumoto

Junji Tanaka

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

Takehiko Yamato


Polymethyl substituted [3.3]metacyclophanes (MCPs) 4 a–d, were synthesized by the TosMIC coupling method followed by Wolff–Kishner reduction of the corresponding polymethyl-substituted [3.3]MCP-2,11-diones (3 a–d). 1H NMR spectroscopy reveals that both 5,6,7,14,16-pentamethyl[3.3]MCP-2,11-diones (3 a and 3 b) undergo conformational changes relative to the NMR time scale in solution at room temperature but that the anti conformer is preferred. Reduced 5,6,7,14,16-pentamethyl[3.3]MCP (4 a and 4 b) adopt fixed syn–conformations in solution at room temperature. X-ray analysis showed that in the solid state, 5,6,7,14,15,16-hexamethyl[3.3]MCP-2,11-dione 3 a adopts the anti-conformation and reduced 5,6,7,14,16-pentamethyl[3.3]MCP-2,11-diones 4 b adopts a syn-(chair-chair) conformation. A series of electrophilic substitution reactions such as formylation, acetylation and nitration were carried out with 5,6,7,14,16-pentamethyl[3.3]MCP 4 b to study their conformational isomers. The formyl, acetyl and nitro derivatives of 5,6,7,14,16-pentamethyl[3.3]MCP are fixed to adopt syn-conformations in solution at room temperature. The conformational isomers of the metacyclophanes and derivatives obtained from density functional theory (DFT) methods were used to estimate the total energies and energy minimized structures of the different conformations.


Islam, M. M., Akther, T., Rahman, S., Georghiou, P. E., Matsumoto, T., Tanaka, J., …Yamato, T. (2017). Synthesis, Conformational Properties and DFT Computational Studies of Polymethyl-Substituted [3.3]Metacyclophanes. ChemistrySelect, 2(24), 7255-7262.

Journal Article Type Article
Acceptance Date Jul 28, 2017
Online Publication Date Aug 23, 2017
Publication Date Aug 22, 2017
Deposit Date Dec 8, 2020
Journal ChemistrySelect
Electronic ISSN 2365-6549
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 2
Issue 24
Pages 7255-7262
Keywords Anti-syn isomerisation; Conformation; DFT calculations; Metacyclophanes; Wolff–Kishner reduction
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