Synthesis, structures and conformational studies of 1,2-dimethyl[2.10]metacyclophane-1-enes

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

Abstract

A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.

Citation

Akther, T., Islam, M. M., Rahman, S., Georghiou, P. E., Matsumoto, T., Tanaka, J., Thuéry, P., Redshaw, C., & Yamato, T. (2016). Synthesis, structures and conformational studies of 1,2-dimethyl[2.10]metacyclophane-1-enes. ChemistrySelect, 1(13), 3594-3600. https://doi.org/10.1002/slct.201600670

• Journal Article Type: Article
• Acceptance Date: Jul 22, 2016
• Online Publication Date: Aug 19, 2016
• Publication Date: Aug 16, 2016
• Deposit Date: Dec 19, 2016
• Publicly Available Date: Dec 19, 2016
• Journal: ChemistrySelect
• Electronic ISSN: 2365-6549
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 1
• Issue: 13
• Pages: 3594-3600
• DOI: https://doi.org/10.1002/slct.201600670
• Keywords: Metacyclophane derivatives, Demethylation, McMurry cyclization, Conformational studies, Intramolecular hydrogen bond
• Public URL: https://hull-repository.worktribe.com/output/446189
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/slct.201600670/abstract;jsessionid=DFE8A09A12C0B772E2576B3079DF37CA.f04t04
• Additional Information: This is the peer reviewed version of the following article: T. Akther, M. M. Islam, S. Rahman, P. E. Georghiou, T. Matsumoto, J. Tanaka, P. Thuéry, C. Redshaw, T. Yamato, ChemistrySelect 2016, 1, 3594, which has been published in final form at http://dx.doi.org/ 10.1002/slct.201600670. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
• Contract Date: Dec 19, 2016