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Oxygen-Oxygen Bond-Forming Reactions for the Synthesis of Cyclic Peroxides
Farhan A Chowdhury1, Elena J Helm1, K A Woerpel1
1Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
None:
Treatment of hydroperoxides bearing pendant hydroxyl groups (OH groups) with sulfonyl chlorides under basic conditions formed cyclic peroxides. Mechanistic experiments indicated that these reactions proceeded by an oxygen-oxygen bond-forming substitution reaction, where the two oxygen atoms take opposite roles: one oxygen atom serves as an electrophile, and the other serves as a nucleophile. This mechanism was supported by 17O-labeling experiments and by the determination that the reaction proceeds with retention of configuration at the carbon atoms of the ring. The reaction was rapid at -78 °C, it was high-yielding, and it was general for a range of substrates, including the formation of five- and six-membered cyclic and bicyclic peroxides. This reaction, therefore, serves as a synthetic analogy to the oxygen-oxygen bond formation reaction used in nature to form dioxygen.
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