Synthesis and conformational studies of chiral macrocyclic [1.1.1]metacyclophanes containing benzofuran rings

Md Monarul Islam, Hirotsugu Tomiyasu, Taisuke Matsumoto, Junji Tanaka, Shofiur Rahman, Paris E. Georghiou, Carl Redshaw, Takehiko Yamato

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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.

Original languageEnglish
Pages (from-to)9055-9064
Number of pages10
JournalOrganic and Biomolecular Chemistry
Volume13
Issue number34
DOIs
Publication statusPublished - Jul 17 2015

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All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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