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

Thamina Akther, Md Monarul Islam, Taisuke Matsumoto, Junji Tanaka, Pierre Thuéry, Carl Redshaw, Takehiko Yamato

Research output: Contribution to journalArticle

1 Citation (Scopus)

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-Br3 in dry CH2Cl2 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 CH2Cl2 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.

Original languageEnglish
Pages (from-to)329-335
Number of pages7
JournalTetrahedron
Volume74
Issue number2
DOIs
Publication statusPublished - Jan 11 2018

Fingerprint

Bridged-Ring Compounds
Aromatization
Enantiomers
Chirality
Halogenation
Circular Dichroism
Mirrors
pyridine
acetylenedicarboxylic acid dimethyl ester
butane
titanium tetrachloride

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Akther, T., Islam, M. M., Matsumoto, T., Tanaka, J., Thuéry, P., Redshaw, C., & Yamato, T. (2018). Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane. Tetrahedron, 74(2), 329-335. https://doi.org/10.1016/j.tet.2017.11.075

Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane. / Akther, Thamina; Islam, Md Monarul; Matsumoto, Taisuke; Tanaka, Junji; Thuéry, Pierre; Redshaw, Carl; Yamato, Takehiko.

In: Tetrahedron, Vol. 74, No. 2, 11.01.2018, p. 329-335.

Research output: Contribution to journalArticle

Akther, T, Islam, MM, Matsumoto, T, Tanaka, J, Thuéry, P, Redshaw, C & Yamato, T 2018, 'Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane', Tetrahedron, vol. 74, no. 2, pp. 329-335. https://doi.org/10.1016/j.tet.2017.11.075
Akther T, Islam MM, Matsumoto T, Tanaka J, Thuéry P, Redshaw C et al. Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane. Tetrahedron. 2018 Jan 11;74(2):329-335. https://doi.org/10.1016/j.tet.2017.11.075
Akther, Thamina ; Islam, Md Monarul ; Matsumoto, Taisuke ; Tanaka, Junji ; Thuéry, Pierre ; Redshaw, Carl ; Yamato, Takehiko. / Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane. In: Tetrahedron. 2018 ; Vol. 74, No. 2. pp. 329-335.
@article{2950987db5af4bd59834a11a173bfd40,
title = "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-Br3 in dry CH2Cl2 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 CH2Cl2 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.",
author = "Thamina Akther and Islam, {Md Monarul} and Taisuke Matsumoto and Junji Tanaka and Pierre Thu{\'e}ry and Carl Redshaw and Takehiko Yamato",
year = "2018",
month = "1",
day = "11",
doi = "10.1016/j.tet.2017.11.075",
language = "English",
volume = "74",
pages = "329--335",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
number = "2",

}

TY - JOUR

T1 - Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane

AU - Akther, Thamina

AU - Islam, Md Monarul

AU - Matsumoto, Taisuke

AU - Tanaka, Junji

AU - Thuéry, Pierre

AU - Redshaw, Carl

AU - Yamato, Takehiko

PY - 2018/1/11

Y1 - 2018/1/11

N2 - 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-Br3 in dry CH2Cl2 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 CH2Cl2 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.

AB - 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-Br3 in dry CH2Cl2 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 CH2Cl2 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.

UR - http://www.scopus.com/inward/record.url?scp=85036652024&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85036652024&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2017.11.075

DO - 10.1016/j.tet.2017.11.075

M3 - Article

VL - 74

SP - 329

EP - 335

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 2

ER -