Persulfoxide: key intermediate in reactions of singlet oxygen with sulfides.
Persulfoxide (R(2)S(+)-OO(-) <--> R(2)S(.)-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.
Clennan
E L
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Department of Chemistry, University of Wyoming, Laramie, WY 82071, USA.
D001713:Biphenyl Compounds / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000737:chemistry; D003499:Cyclic S-Oxides / Q000737:chemistry; D005027:Ethylene Oxide / Q000031:analogs & derivatives / Q000737:chemistry; D012451:Safrole / Q000031:analogs & derivatives* / Q000737:chemistry*; D017640:Silicates / Q000737:chemistry; D026082:Singlet Oxygen / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry*
D001713:Biphenyl Compounds; D001952:Bridged-Ring Compounds; D003499:Cyclic S-Oxides; D017640:Silicates; D013440:Sulfides; C051552:persulfides; D026082:Singlet Oxygen; D005027:Ethylene Oxide; D012451:Safrole; C005746:sulfoxide