Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 77, Issue 3, Pages 1233-1243Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo202265j
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Funding
- NSF [CHE-0749916, -1057982]
- NIH [RR016544]
- University of Illinois [CHE090078]
- Hope College [NSF-CHE-0520704]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1057982] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1039925] Funding Source: National Science Foundation
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The first singlet excited state of molecular oxygen (O-1(2)) is an important oxidant in chemistry, biology, and medicine. O-1(2) is most often generated through photosensitized excitation of ground-state oxygen. O-1(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 O-1(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 (O-1(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.
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