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 b‐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.