Silylstannanes in Organic Synthesis. Scope and Limitation of Palladium-Catalyzed Reaction with Acetylenes

Article abstract of DOI:10.1021/jo00369a001

Terminal acetylenes react with silylstannanes in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium to give highly regio- and stereoselective addition (cis addition with tin always adding to the internal position).The process is general and tolerates a number of functional groups including Cl, OH, OTHP, and CN.With propargyl substitution, however, the reaction is not useful.Several reactions of silyl tin olefins (transmetalation, halogenation, and AlCl3-catalyzed acylation) are described.These reactions allow useful organic fragments (or halogen) to be introduced while generally retaining the silicon moiety available for further manipulation