Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides

Jiliang Hang, Prasanta Ghorai, Solaire A. Finkenstaedt-Quinn, Ilhan Findik, Emily Sliz, Keith T. Kuwata, Patrick H Dussault

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The first singlet excited state of molecular oxygen ( 1O 2) is an important oxidant in chemistry, biology, and medicine. 1O 2 is most often generated through photosensitized excitation of ground-state oxygen. 1O 2 can also be generated chemically through the decomposition of hydrogen peroxide and other peroxides. However, most of these "dark oxygenations" require water-rich media associated with short 1O 2 lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen ( 1O 2). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and a peroxide activated toward heterolytic cleavage. The reaction is general for a range of skeletal frameworks and activating groups and, via in situ activation, can be applied directly to 1,1-dihydroperoxides. Our investigation suggests the fragmentation involves rate-limiting formation of a peroxyanion that decomposes via a Grob-like process.

Original languageEnglish (US)
Pages (from-to)1233-1243
Number of pages11
JournalJournal of Organic Chemistry
Volume77
Issue number3
DOIs
StatePublished - Feb 3 2012

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Singlet Oxygen
Oxygenation
Molecular oxygen
Peroxides
Organic solvents
Excited states
Oxidants
Ground state
Hydrogen Peroxide
Medicine
Chemical activation
Oxygen
Derivatives
Decomposition
Water

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Hang, J., Ghorai, P., Finkenstaedt-Quinn, S. A., Findik, I., Sliz, E., Kuwata, K. T., & Dussault, P. H. (2012). Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides. Journal of Organic Chemistry, 77(3), 1233-1243. https://doi.org/10.1021/jo202265j

Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides. / Hang, Jiliang; Ghorai, Prasanta; Finkenstaedt-Quinn, Solaire A.; Findik, Ilhan; Sliz, Emily; Kuwata, Keith T.; Dussault, Patrick H.

In: Journal of Organic Chemistry, Vol. 77, No. 3, 03.02.2012, p. 1233-1243.

Research output: Contribution to journalArticle

Hang, J, Ghorai, P, Finkenstaedt-Quinn, SA, Findik, I, Sliz, E, Kuwata, KT & Dussault, PH 2012, 'Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides', Journal of Organic Chemistry, vol. 77, no. 3, pp. 1233-1243. https://doi.org/10.1021/jo202265j
Hang J, Ghorai P, Finkenstaedt-Quinn SA, Findik I, Sliz E, Kuwata KT et al. Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides. Journal of Organic Chemistry. 2012 Feb 3;77(3):1233-1243. https://doi.org/10.1021/jo202265j
Hang, Jiliang ; Ghorai, Prasanta ; Finkenstaedt-Quinn, Solaire A. ; Findik, Ilhan ; Sliz, Emily ; Kuwata, Keith T. ; Dussault, Patrick H. / Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides. In: Journal of Organic Chemistry. 2012 ; Vol. 77, No. 3. pp. 1233-1243.
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