Fe(II)-mediated fragmentation of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes through competitive single electron transfer pathway and Lewis acid pathway

Masaki Kamata, Takashi Kudoh, Jun Ichi Kaneko, Hye-Sook Kim, Yusuke Wataya

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Reactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes 1a-d (1a: Ar=p-FC6H4, 1b: Ar=Ph, 1c: Ar=p-MeC6H4, 1d: Ar=p-MeOC6H4) with FeBr2 in THF afforded 1,4-diarylbutan-1,4-diones 2a-d and 1,4-diaryl-7-oxabicyclo[2.2.1]heptanes 3a-d. On the other hand, 4-aryl-3-cyclohexenones 4c-d and p-substituted phenols 5c-d were obtained in the reactions of 1c-d with FeBr2 in CH2Cl2. A new fragmentation mechanism involving an electrophilic oxyl radical 1,5-substitution and a nucleophilic O-1,2-aryl shift is proposed based on the product analysis. In addition, the in vitro antimalarial activities of 1a-d were tested.

Original languageEnglish
Pages (from-to)617-620
Number of pages4
JournalTetrahedron Letters
Volume43
Issue number4
DOIs
Publication statusPublished - Jan 21 2002

Fingerprint

Octanes
Lewis Acids
Phenols
Antimalarials
Substitution reactions
Electrons
7-oxabicyclo(2.2.1)heptane
In Vitro Techniques

Keywords

  • 1,2-aryl shift
  • 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes
  • Antimalarial activity
  • Cyclic peroxides
  • FeBr
  • Fragmentation
  • Reaction mechanism

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Fe(II)-mediated fragmentation of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes through competitive single electron transfer pathway and Lewis acid pathway. / Kamata, Masaki; Kudoh, Takashi; Kaneko, Jun Ichi; Kim, Hye-Sook; Wataya, Yusuke.

In: Tetrahedron Letters, Vol. 43, No. 4, 21.01.2002, p. 617-620.

Research output: Contribution to journalArticle

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abstract = "Reactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes 1a-d (1a: Ar=p-FC6H4, 1b: Ar=Ph, 1c: Ar=p-MeC6H4, 1d: Ar=p-MeOC6H4) with FeBr2 in THF afforded 1,4-diarylbutan-1,4-diones 2a-d and 1,4-diaryl-7-oxabicyclo[2.2.1]heptanes 3a-d. On the other hand, 4-aryl-3-cyclohexenones 4c-d and p-substituted phenols 5c-d were obtained in the reactions of 1c-d with FeBr2 in CH2Cl2. A new fragmentation mechanism involving an electrophilic oxyl radical 1,5-substitution and a nucleophilic O-1,2-aryl shift is proposed based on the product analysis. In addition, the in vitro antimalarial activities of 1a-d were tested.",
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T1 - Fe(II)-mediated fragmentation of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes through competitive single electron transfer pathway and Lewis acid pathway

AU - Kamata, Masaki

AU - Kudoh, Takashi

AU - Kaneko, Jun Ichi

AU - Kim, Hye-Sook

AU - Wataya, Yusuke

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AB - Reactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes 1a-d (1a: Ar=p-FC6H4, 1b: Ar=Ph, 1c: Ar=p-MeC6H4, 1d: Ar=p-MeOC6H4) with FeBr2 in THF afforded 1,4-diarylbutan-1,4-diones 2a-d and 1,4-diaryl-7-oxabicyclo[2.2.1]heptanes 3a-d. On the other hand, 4-aryl-3-cyclohexenones 4c-d and p-substituted phenols 5c-d were obtained in the reactions of 1c-d with FeBr2 in CH2Cl2. A new fragmentation mechanism involving an electrophilic oxyl radical 1,5-substitution and a nucleophilic O-1,2-aryl shift is proposed based on the product analysis. In addition, the in vitro antimalarial activities of 1a-d were tested.

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