Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes: Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes

Thuéry, Pierre; Islam, Md Monarul; Akther, Thamina; Islam, Md. Monarul; Matsumoto, Taisuke; Tanaka, Junji; Thuery, Pierre; Redshaw, Carl; Yamato, Takehiko

Abstract

Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of 2 with Zn and AcOH in CH₂Cl solution at room temperature for 24 h produced dimethylene[2.10]MCP 7 in 92 % yield, which is a stable solid compound. Compound 7 was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate (8) in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate 9, possessing C₁ symmetry, by aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). A new type of N-phenyl-maleimide substituted 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-N-phenylmaleimide 10 was also synthesized from 7 through treatment with N-phenylmaleimide in toluene at 110 °C followed by aromatization with DDQ. Single-crystal X-ray analysis of 9 revealed the formation of a syn-isomer.

Citation

Thuéry, P., Islam, M. M., Akther, T., Islam, M. M., Matsumoto, T., Tanaka, J., …Yamato, T. (2017). Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes: Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes. European Journal of Organic Chemistry, 2017(13), 1721-1726. https://doi.org/10.1002/ejoc.201601647

• Acceptance Date: Jan 23, 2017
• Online Publication Date: Apr 4, 2017
• Publication Date: Apr 3, 2017
• Deposit Date: May 9, 2017
• Publicly Available Date: Jan 24, 2018
• Journal: European journal of organic chemistry
• Print ISSN: 1434-193x
• Electronic ISSN: 1099-0690
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 2017
• Issue: 13
• Pages: 1721-1726
• DOI: https://doi.org/10.1002/ejoc.201601647
• Keywords: 1,2-Dimethylene[2.10]metacyclophane; Chiral [10]Benzenometacyclophanes
• Public URL: https://hull-repository.worktribe.com/output/451187
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201601647/abstract;jsessionid=F778D40570FE9CE95602C913F33EA45D.f02t02
• Additional Information: Authors' accepted manuscript of article: Akther, T., Islam, Md. M., Matsumoto, T., Tanaka, J., Thuéry, P., Redshaw, C. and Yamato, T. (2017), Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes. Eur. J. Org. Chem., 2017: 1721–1726. doi:10.1002/ejoc.201601647