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Persulfoxide: Key Intermediate in Reactions of Singlet Oxygen with Sulfides

2001; American Chemical Society; Volume: 34; Issue: 11 Linguagem: Inglês

10.1021/ar0100879

1520-4898

Edward L. Clennan,

Radical Photochemical Reactions

Persulfoxide (R2S+−OO- ↔ R2S•−OO•) is the first formed intermediate in the reactions between singlet oxygen and organic sulfides. It is a weakly bound species that nevertheless has a sufficient lifetime to undergo a myriad of inter- and intramolecular reactions. Its behavior suggests that it can be considered as a resonance hybrid of zwitterionic and diradical canonical structures. It primarily acts as a nucleophile/base at oxygen but has a tendency to interconvert to secondary intermediates that often behave as electrophilic oxidizing agents. Judicious selection of reaction conditions and substituents can allow the use of the persulfoxide as a synthetically useful intermediate.