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

17 Scopus citations

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

ASJC Scopus subject areas

  • Organic Chemistry

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    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