Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane - CEA - Commissariat à l’énergie atomique et aux énergies alternatives Access content directly
Journal Articles Tetrahedron Year : 2018

Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane

Abstract

The reductive coupling reaction of 1,4-bis(3-acetyl-5-tert-butyl-2-methoxyphenyl)butane 3 was carried out using TiCl4-Zn in pyridine followed by a McMurry coupling reaction to afford the compounds anti and syn 1,2-dimethyl[2.4]MCP-1-ene 4. Bromination of 4 with BTMA-Br$_3$ in dry CH$_2$Cl$_2$ afforded the interesting compound 1,2-bis-(bromomethyl)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-1-ene 6 and consecutive debromination with Zn and AcOH in CH2$_C$l$_2$ solution afforded the stable solid 5,15-di-tert-butyl-8,18-dimethoxy-1,2-dimethylene[2.4]MCP 7 in 89% yield. Compound 7 was conveniently employed in a Diels–Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to provide 2-(3′,6′-dihydrobenzo)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-4′,5′-dimethylcarboxylate 8 in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged compound [2.4]MCP 9 by aromatization. The chirality of the two conformers was characterized by circular dichroism (CD) spectra of the separated enantiomer which are perfect mirror images of each other.
Fichier principal
Vignette du fichier
Thuery_Tet2017_V0.pdf (1.06 Mo) Télécharger le fichier
Origin : Files produced by the author(s)
Loading...

Dates and versions

cea-01656007 , version 1 (13-12-2017)

Identifiers

Cite

Thamina Akhter, Md. Monarul Islam, Taisuke Matsumoto, Junji Tanaka, Pierre Thuéry, et al.. Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane. Tetrahedron, 2018, 74, pp.329-335. ⟨10.1016/j.tet.2017.11.075⟩. ⟨cea-01656007⟩
236 View
138 Download

Altmetric

Share

Gmail Facebook X LinkedIn More