Generation of Singlet Oxygen from Fragmentation of Monoactivated 1,1-Dihydroperoxides

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• 作者：Jiliang Hang ; Prasanta Ghorai ; Solaire A. Finkenstaedt-Quinn ; Ilhan Findik ; Emily Sliz ; Keith T. Kuwata ; Patrick H. Dussault
• 刊名：The Journal of Organic Chemistry
• 出版年：2012
• 出版时间：February 3, 2012
• 年：2012
• 卷：77
• 期：3
• 页码：1233-1243
• 全文大小：620K
• 年卷期：v.77,no.3(February 3, 2012)
• ISSN：1520-6904

文摘

The first singlet excited state of molecular oxygen (¹O₂) 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 鈥渄ark oxygenations鈥?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.