Synthesis and structure of 1,2-dimethylene[2.10]metacyclophane and its conversion to chiral [10]benzenometacyclophanes

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 the identical dimethylene[2.10]MCP 7 in 92% yield, which is a stable solid compound. Subsequently, compound 7 was reacted 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 to a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4',5'-dimethylcarboxylate 9 by aromatization with dichlorodicyano-p-benzoquinone (DDQ), possessing  C1 symmetry. Also 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 synthesised from 7 via treatment with N-phenylmaleimide in toluene at 110°C followed by aromatization with DDQ. Single crystal X-ray analysis of 9 revealed the adoption of a syn-isomer.
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European Journal of Organic Chemistry, Wiley-VCH Verlag, 2017, 2017, pp.1721-1726. 〈http://dx.doi.org/10.1002/ejoc.201601647〉. 〈10.1002/ejoc.201601647〉
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https://hal-cea.archives-ouvertes.fr/cea-01478246
Contributeur : Serge Palacin <>
Soumis le : mardi 28 février 2017 - 08:16:01
Dernière modification le : jeudi 15 mars 2018 - 15:05:40

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Thamina Akhter, Md Monarul Islam, Taisuke Matsumoto, Junji Tanaka, Pierre Thuéry, et al.. Synthesis and structure of 1,2-dimethylene[2.10]metacyclophane and its conversion to chiral [10]benzenometacyclophanes. European Journal of Organic Chemistry, Wiley-VCH Verlag, 2017, 2017, pp.1721-1726. 〈http://dx.doi.org/10.1002/ejoc.201601647〉. 〈10.1002/ejoc.201601647〉. 〈cea-01478246〉

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