Inversion of Reactivity (umpolung) of Carbonyl Compounds Using Organosulfur Compounds Reagents


Abstract in English

Organosulfur compounds have been exploited to reverse the reactivity of carbonyl compounds. The heteroatom produces a reactivity pattern in a carbon skeleton. Its electronegativity, being greater than that of carbon (-I effect) and its ability to stabilize an adjacent positive charge (+M effect) makes the sites susceptible to be attacked by reagents possessing a given “philicity”. Nucleophiles attacks the odd C atomes ( 1,3,5... C attack) whereas electrophiles attacks the even C atomes ( 2,4,6... C attack) of the carbonyl compounds. If the reactivity of a carbonyl could be reversed, the acyl carbon would become nucleophilic, and if this transformation can be accomplished, the carbonyl should be regenerated. Seebach termed this process ''umpolung''.

References used

E.J.Corey, pure. Appl. Chem,14, 1967 , 19
D.A.Evans and G.C.Andreus, Accounts. Chem. Research, 7, 1974,147
D.Seebach, Angew. Chem. Int.Ed.Engl, 18, 1979,239

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