Synthesis and conformations of [2.n]metacyclophan-1-ene epoxides and their conversion to [n.1]metacyclophanes

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

Abstract

A series of syn- and anti-[2.n]metacyclophan-1-enes have been prepared in good yields by McMurry cyclizations of 1,n-bis(5-tert-butyl-3-formyl-2-methoxyphenyl)alkanes. Significantly, acid catalyzed rearrangements of [2.n]metacyclophan-1-enes afforded [n.1]metacyclophanes in good yield. The ratios of the products are strongly regulated by the number of methylene bridges present. The percentages of the rearrangement products increase with increasing length of the carbon bridges. Characterization and the conformational studies of these products are described. Single crystal X-ray analysis revealed the adoption of syn- and anti-conformations. DFT calculations were carried out to estimate the energy-minimized structures of the synthesized metacyclophanes.

Citation

Akther, T., Islam, M. M., Rahman, S., Georghiou, P. E., Matsumoto, T., Tanaka, J., …Yamato, T. (2017). Synthesis and conformations of [2.n]metacyclophan-1-ene epoxides and their conversion to [n.1]metacyclophanes. Organic & biomolecular chemistry, 15(16), 3519-3527. https://doi.org/10.1039/C7OB00400A

• Acceptance Date: Mar 29, 2017
• Online Publication Date: Mar 31, 2017
• Publication Date: Apr 28, 2017
• Deposit Date: May 8, 2017
• Publicly Available Date: Apr 3, 2018
• Journal: Organic & biomolecular chemistry
• Print ISSN: 1477-0520
• Electronic ISSN: 1477-0539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 15
• Issue: 16
• Pages: 3519-3527
• DOI: https://doi.org/10.1039/C7OB00400A
• Keywords: Epoxides; Metacyclophanes
• Public URL: https://hull-repository.worktribe.com/output/451155
• Publisher URL: http://pubs.rsc.org/en/Content/ArticleLanding/2017/OB/C7OB00400A#!divAbstract
• Additional Information: This is the accepted manuscript of an article published in Organic & biomolecular chemistry, 2017. The version of record is available at the DOI link in this record.