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A pummerer type rearrangement during attempted oxidation with dimethyl sulfoxide and dicyclohexyl carbodiimide

✍ Scribed by J. Bryan Jones; Donald C. Wigfield


Publisher
Elsevier Science
Year
1965
Tongue
French
Weight
222 KB
Volume
6
Category
Article
ISSN
0040-4039

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✦ Synopsis


We wish to report the formation of the methylthiomethoxy derivative IV during attempted oxidation of 3S-hydroxyandrost-5-en-l7-one(I) with dimethylsulfoxide (DMSO) and dicyclohexylcarbodiimide (DCC). Compound IV presumably arises by rearrangement of the intermediate sulfoniumoxy salt III. (Dimethylsulfoniumoxy salts of this type have been postulated as intermediates in oxidations involving DMSO (1,2),) This rearrangement, where C to 0 migration is + accompanied by rupture of the S-O bond, resembles the Pummerer reaction (3) in which sulfoxides react with acetic anhydride to give a-acetoxysulfides. However, as the latter