Md Monarul Islam
Synthesis and conformational studies of chiral macrocyclic [1.1.1]metacyclophanes containing benzofuran rings
Islam, Md Monarul; Tomiyasu, Hirotsugu; Matsumoto, Taisuke; Tanaka, Junji; Rahman, Shofiur; Georghiou, Paris E.; Redshaw, Carl; Yamato, Takehiko
Authors
Hirotsugu Tomiyasu
Taisuke Matsumoto
Junji Tanaka
Shofiur Rahman
Paris E. Georghiou
Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry
Takehiko Yamato
Abstract
Macrocyclic [1.1.1]metacyclophanes (MCPs) containing benzene and benzofuran rings linked by methylene bridges and which can be viewed as calixarene analogues, have been synthesized by demethylation of [3.3.1]MCP-diones with trimethylsilyl iodide (TMSI) in MeCN. The [3.3.1]MCP-diones are synthesized by using (p-tolylsulfonyl)methyl isocyanide (TosMIC) as the cyclization reagent in N,N-dimethylformamide (DMF) with an excess of sodium hydride. ¹H NMR spectroscopy revealed that the remaining hydroxyl group on the phenyl ring is involved in intramolecular hydrogen bonding with the oxygen of one of the benzofuran rings. O-Methylation at the lower rim of monohydroxy[1.1.1]MCP in the presence of K₂CO₃ in acetone afforded a novel and inherently chiral calixarene analogue, namely the macrocyclic [1.1.1]MCP, 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, which caused a splitting of the corresponding methylene protons to AB patterns. Single crystal X-ray analysis revealed the adoptation of a hemisphere-shaped cone isomer. DFT calculations were carried out to investigate the energy-minimized structures and the hydrogen bonds of the synthesized MCPs.
Citation
Islam, M. M., Tomiyasu, H., Matsumoto, T., Tanaka, J., Rahman, S., Georghiou, P. E., …Yamato, T. (2015). Synthesis and conformational studies of chiral macrocyclic [1.1.1]metacyclophanes containing benzofuran rings. Organic & biomolecular chemistry, 13(34), 9055-9064. https://doi.org/10.1039/c5ob01002k
Journal Article Type | Article |
---|---|
Acceptance Date | Jul 17, 2015 |
Online Publication Date | Jul 20, 2015 |
Publication Date | Jul 20, 2015 |
Deposit Date | Jul 22, 2015 |
Publicly Available Date | Mar 29, 2024 |
Journal | Organic and biomolecular chemistry |
Print ISSN | 1477-0520 |
Electronic ISSN | 1477-0539 |
Publisher | Royal Society of Chemistry |
Peer Reviewed | Peer Reviewed |
Volume | 13 |
Issue | 34 |
Pages | 9055-9064 |
DOI | https://doi.org/10.1039/c5ob01002k |
Keywords | Benzofuran rings , Macrocyclic [1.1.1]metacyclophanes , MCPs |
Public URL | https://hull-repository.worktribe.com/output/376712 |
Publisher URL | http://pubs.rsc.org/en/Content/ArticleLanding/2015/OB/C5OB01002K#!divAbstract |
Additional Information | Authors' accepted manuscript of article published in: Organic and biomolecular chemistry, 2015 at http://pubs.rsc.org/en/Content/ArticleLanding/2015/OB/C5OB01002K#!divAbstract |
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