Synthesis and conformational studies of calixarene analogue chiral [3.3.1]metacyclophanes

Islam, Md Monarul; Hirotsugu, Tomiyasu; Thuery, Pierre; Matsumoto, Taisuke; Tanaka, Junji; Elsegood, Mark R.J.; Redshaw, Carl; Yamato, Takehiko

Abstract

Trihydroxy[3.3.1]metacyclophane, which can be regarded as an unsymmetrical or incomplete “homocalix[3]arene”, has been prepared from trimethoxy[3.3.1]metacyclophane by demethylation with trimethylsilyl iodide in MeCN. Di-O-methylation at the lower rim of trihydroxy[3.3.1]metacyclophane in the presence of K₂CO₃ in acetone afforded a novel, inherently chiral calixarene–analogue, namely a macrocyclic [3.3.1]metacyclophane, possessing C₁ symmetry. The inherent chirality of the two conformers was characterized by ¹H NMR spectroscopy by addition of an excess of Pirkle's chiral shift reagent [(S)-(+)-1-(9-anthryl)-2,2,2-trifluoroethanol], which caused a splitting of the OMe group and AB patterns corresponding to the methylene protons.

Citation

Islam, M. M., Hirotsugu, T., Thuery, P., Matsumoto, T., Tanaka, J., Elsegood, M. R., Redshaw, C., & Yamato, T. (2015). Synthesis and conformational studies of calixarene analogue chiral [3.3.1]metacyclophanes. Journal of molecular structure, 1098, 47-54. https://doi.org/10.1016/j.molstruc.2015.05.036

• Journal Article Type: Article
• Acceptance Date: May 28, 2015
• Online Publication Date: May 30, 2015
• Publication Date: Sep 15, 2015
• Deposit Date: Mar 15, 2016
• Publicly Available Date: Nov 23, 2017
• Journal: Journal of molecular structure
• Print ISSN: 0022-2860
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 1098
• Pages: 47-54
• DOI: https://doi.org/10.1016/j.molstruc.2015.05.036
• Keywords: Metacyclophanes, Macrocycles, Calixarenes, Intramolecular hydrogen bonding, O–methylation, Chirality
• Public URL: https://hull-repository.worktribe.com/output/471887
• Publisher URL: http://www.sciencedirect.com/science/article/pii/S002228601530020X
• Additional Information: Authors' accepted manuscript of article published in: Journal of molecular structure, 2015, v.1098
• Contract Date: Nov 23, 2017