Dielectrophilic Approach to Sequential Heterofunctionalization of Ethylene from Vinylthianthrenium Salt

Vinyl thianthrenium salt is a compound with interesting electrophilic properties capable of reacting with two distinct nucleophiles. By using beta-keto esters as one of the reaction partners, it is possible to insert a chain of two carbon atoms with a further functionalization under mild conditions. We have studied this new methodology which involves the stepwise formation of a C-C and a C-X bond (with X=N, O, etc.) in one step without the use of metals. Depending on the reaction conditions and the starting ketoester, a varied reactivity has been observed and described. Vinylthianthrenium salt was employed as the starting material for a formal difunctionalization of ethylene. Its 1,2-dielectrophilic property enables the sequential incorporation of two distinct nucleophiles onto ethylene. Through this method, we achieve the formation of a C-C bond and a C-X bond (X=N, O, halogen) on ethylene, in a single step performed under mild conditions. image