Sensitized photooxygenation of 6-heteroatom-substituted fulvenes

Primary products and their chemical transformations

Xiaojun Zhang, Feng Lin, Christopher S. Foote

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Sensitized photooxygenation of 6,6-diethoxyfulvene (1) and 6,6-(ethylenedithio)fulvene (9) at -78 °C afforded diethoxyfulvene endoperoxide 2 and (ethylenedithio)fulvene endoperoxide 10, respectively, as primary products. Further irradiation resulted in formation of the novel bisperoxides 3 and 11 from [2 + 2] cycloaddition of 1O2 to the exocyclic double bond of the corresponding endoperoxides. The initial endoperoxides were characterized by NMR at low temperature and underwent a variety of chemical transformations to give highly oxygenated cyclopentane derivatives. In contrast, photooxygenation of 6,6-dipiperidinofulvene (16) and 6-(dimethylamino)fulvene (17) did not lead to chemical reaction; these compounds physically quench 1O2 with rate constants on the order of 108 M-1 s-1.

Original languageEnglish (US)
Pages (from-to)1333-1338
Number of pages6
JournalJournal of Organic Chemistry
Volume60
Issue number5
StatePublished - 1995

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Cyclopentanes
Cycloaddition
Chemical reactions
Rate constants
Nuclear magnetic resonance
Irradiation
Derivatives
fulvene
Temperature

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Sensitized photooxygenation of 6-heteroatom-substituted fulvenes : Primary products and their chemical transformations. / Zhang, Xiaojun; Lin, Feng; Foote, Christopher S.

In: Journal of Organic Chemistry, Vol. 60, No. 5, 1995, p. 1333-1338.

Research output: Contribution to journalArticle

Zhang, Xiaojun ; Lin, Feng ; Foote, Christopher S. / Sensitized photooxygenation of 6-heteroatom-substituted fulvenes : Primary products and their chemical transformations. In: Journal of Organic Chemistry. 1995 ; Vol. 60, No. 5. pp. 1333-1338.
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