The Chemistry of Cyclic Peroxides: The Formation and Decomposition of Prostaglandin Endoperoxide Analogs
1978; American Chemical Society; Linguagem: Inglês
10.1021/bk-1978-0069.ch006
ISSN1947-5918
AutoresNed A. Porter, John Nixon, Dennis Gilmore,
Tópico(s)Metal complexes synthesis and properties
ResumoTwo aspects of the chemistry of cyclic peroxides have been investigated. Alkyl radicals β to the peroxide linkage in cyclic peroxides attack the peroxide linkage in an SHi manner giving rise to epoxy-alcohols. The ease of this SHi reaction is dependent on the geometric arrangement of the attacking radical center and the peroxide bond. The preferred geometry appears to be an arrangement in which oxygen leaves by backside displacement from the attacking carbon radical. Bicyclic [2.2.1] endoperoxides have been shown to react with Cu2+ to yield β-hydroxy cyclopentanone by an acid catalyzed isomerization. Cu1+ reduces the endoperoxides to 1,3-cyclopentanediol, and it has been shown that thiol/Cu2+ mixtures act as does Cu1+ on the endoperoxide.
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