Synthesis of β‐Enamino Sulfoxides via Cine ‐Substitution of 1‐Chlorovinyl p ‐Tolyl Sulfoxides with Lithium Amides

The cine ‐substitution of 2‐aryl‐1‐chlorovinyl p ‐tolyl sulfoxides with lithium amides of azoles and anilines and sodium amides of imidazole, carboxamide, and aliphatic amine occurs to yield β‐enamino sulfoxides with high efficiency. β‐Elimination–addition is a plausible mechanism for cine ‐substitution. β‐Enamino sulfoxides are desulfinylated via the sulfoxide/magnesium exchange reaction with isopropylmagnesium chloride and the protonation of the resulting (2‐aminovinyl)magnesium chlorides. N ‐(α‐Styryl)indole is prepared from indole and 1‐chloro‐2‐phenylvinyl p ‐tolyl sulfoxide through a one‐pot procedure involving cine ‐substitution and desulfinylation.