Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes

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

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room temperature for 24 h produced dimethylene[2.10]MCP 7 in 92 % yield, which is a stable solid compound. Compound 7 was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate (8) in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate 9, possessing C1 symmetry, by aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). A new type of N-phenyl-maleimide substituted 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-N-phenylmaleimide 10 was also synthesized from 7 through treatment with N-phenylmaleimide in toluene at 110 °C followed by aromatization with DDQ. Single-crystal X-ray analysis of 9 revealed the formation of a syn-isomer.

Original languageEnglish
Pages (from-to)1721-1726
Number of pages6
JournalEuropean Journal of Organic Chemistry
Volume2017
Issue number13
DOIs
Publication statusPublished - Jan 1 2017

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Aromatization
bromination
X ray analysis
Toluene
quinones
synthesis
Isomers
adducts
toluene
isomers
Single crystals
single crystals
symmetry
room temperature
x rays
Temperature
N-phenylmaleimide
dichlorodicyanobenzoquinone
benzyltrimethylammonium
acetylenedicarboxylic acid dimethyl ester

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes. / Akther, Thamina; Islam, Md Monarul; Matsumoto, Taisuke; Tanaka, Junji; Thuéry, Pierre; Redshaw, Carl; Yamato, Takehiko.

In: European Journal of Organic Chemistry, Vol. 2017, No. 13, 01.01.2017, p. 1721-1726.

Research output: Contribution to journalArticle

Akther, Thamina ; Islam, Md Monarul ; Matsumoto, Taisuke ; Tanaka, Junji ; Thuéry, Pierre ; Redshaw, Carl ; Yamato, Takehiko. / Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes. In: European Journal of Organic Chemistry. 2017 ; Vol. 2017, No. 13. pp. 1721-1726.
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abstract = "Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room temperature for 24 h produced dimethylene[2.10]MCP 7 in 92 {\%} yield, which is a stable solid compound. Compound 7 was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate (8) in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate 9, possessing C1 symmetry, by aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). A new type of N-phenyl-maleimide substituted 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-N-phenylmaleimide 10 was also synthesized from 7 through treatment with N-phenylmaleimide in toluene at 110 °C followed by aromatization with DDQ. Single-crystal X-ray analysis of 9 revealed the formation of a syn-isomer.",
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T1 - Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes

AU - Akther, Thamina

AU - Islam, Md Monarul

AU - Matsumoto, Taisuke

AU - Tanaka, Junji

AU - Thuéry, Pierre

AU - Redshaw, Carl

AU - Yamato, Takehiko

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N2 - Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room temperature for 24 h produced dimethylene[2.10]MCP 7 in 92 % yield, which is a stable solid compound. Compound 7 was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate (8) in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate 9, possessing C1 symmetry, by aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). A new type of N-phenyl-maleimide substituted 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-N-phenylmaleimide 10 was also synthesized from 7 through treatment with N-phenylmaleimide in toluene at 110 °C followed by aromatization with DDQ. Single-crystal X-ray analysis of 9 revealed the formation of a syn-isomer.

AB - Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room temperature for 24 h produced dimethylene[2.10]MCP 7 in 92 % yield, which is a stable solid compound. Compound 7 was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate (8) in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate 9, possessing C1 symmetry, by aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). A new type of N-phenyl-maleimide substituted 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-N-phenylmaleimide 10 was also synthesized from 7 through treatment with N-phenylmaleimide in toluene at 110 °C followed by aromatization with DDQ. Single-crystal X-ray analysis of 9 revealed the formation of a syn-isomer.

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