Palladium-Catalyzed Regio- and Stereoselective Synthesis of (E)-1,3-Bissilyl-6-arylfulvenes from Aryl Iodides and Silylacetylenes

Abstract

An efficient synthetic route to ( E)-1,3-bissilyl-6-arylfulvenes has been developed. The reaction of aryl iodides with trimethylsilylacetylene in the presence of a catalytic amount of PdBr2 gives 6-aryl-1,3-bis(trimethylsilyl)fulvenes in good to excellent yields with complete regio- and stereoselectivity. The reaction involves trimerization of trimethylsilylacetylene and cleavage of one silyl group. The silylated fulvenes obtained could be converted into halogenated fulvenes by site-selective halodesilylation. The halogenated fulvenes underwent the Stille coupling leading to the corresponding arylated fulvenes.