Divergent oxidative rearrangements in solution and in a zeolite: Distal vs proximal bond cleavage of methylenecyclopropanes

Hiroshi Ikeda, Tsuyoshi Nomura, Kimio Akiyama, Mitsuhiro Oshima, Heinz D. Roth, Shozo Tero-Kubota, Tsutomu Miyashi

Research output: Contribution to journalArticlepeer-review

19 Citations (Scopus)

Abstract

Irradiation of 9,10-dicyanoanthracene (DCA) or p-chloranil in the presence of E-1-benzylidene-2-phenylcyclopropane (E-5) in CH2CI2 causes E-5 to undergo methylenecyclopropane rearrangement. An adduct, Z-7, between DCA and 5 firmly supports the involvement of a bifunctional trimethylenemethane radical cation. In contrast, incorporation of E-5 into HZSM-5 produces trans,trans-1,4-diphenyl-1,3-butadiene radical cation sequestered in the HZSM-5 interior, tt-8·+ @ HZSM-5, identified by ESR and diffuse reflectance spectroscopy. In addition, low yields of tt-8, its cis, trans-isomer (ct-8), and 1-phenyl-1,2-dihydronaphthalene (9) were isolated from the supernatant solution. The sharp contrast between the photoinduced electrontransfer reaction with photosensitizers in solution and the spontaneous reaction with redox-active acidic zeolite offers the prospect of further zeolite-induced regiodivergent reactions in a range of additional substrates.

Original languageEnglish
Pages (from-to)14497-14504
Number of pages8
JournalJournal of the American Chemical Society
Volume127
Issue number41
DOIs
Publication statusPublished - 2005 Oct 19

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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