1354978-56-5Relevant articles and documents
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.
supporting information; scheme or table, p. 1233 - 1243 (2012/03/27)
The first singlet excited state of molecular oxygen (1O 2) is an important oxidant in chemistry, biology, and medicine. 1O2 is most often generated through photosensitized excitation of ground-state oxygen. 1O2 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 1O2 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 (1O2). 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.
