Sequential Photostimulated Reactions of Trimethylstannyl Anions with Aromatic Compounds Followed by Palladium-Catalyzed Cross-Coupling Processes

The photostimulated reactions of several mono-, di-, and trichloroarenes and aryltrimethylammonium salts with Me₃Sn^- ions in liquid ammonia gave good yields of stannanes by the S_RN1 mechanism. If the chloroarenes are not soluble in liquid ammonia, diglyme is another solvent to perform these reactions. The stannanes thus obtained can be arylated by further reaction with haloarenes through palladium-catalyzed reactions. If the palladium-catalyzed reaction is performed with a chloroiodoarene as substrate, the stannane reacts faster by the C−I bond via chemoselective cross-coupling reaction to give a chloroarene as product, which can be further arylated by a consecutive S_RN1−Stille reaction or react with other substrates by another palladium-catalyzed reaction. These sequential reactions can also be performed with substrates with two leaving groups to give products in high yields.