Oxygen-Oxygen Bond-Forming Reactions for the Synthesis of Cyclic Peroxides.

Abstract

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.