Access to C(sp³)–C(sp²) and C(sp²)–C(sp²) Bond Formation via Sequential Intermolecular Carbopalladation of Multiple Carbon–Carbon Bonds

A synthetic strategy of 4-benzyl-substituted 1,3-butadiene derivatives through Pd-catalyzed three-component coupling reaction of benzyl chlorides, alkynes, and monosubstituted alkenes is described. This tandem coupling reaction forms a C­(sp³)–C­(sp²) bond and a C­(sp²)–C­(sp²) bond sequentially in a single-step operation

Synthesis of δ-Bromo γ,δ-Unsaturated Carbonyl Compounds via Palladium-Catalyzed Bromoalkylation of Alkynoates

Palladium-catalyzed regio- and stereoselective intermolecular tandem reaction of electron-deficient alkynes, CuBr₂, and allylic alcohol to synthesize δ-bromo-γ,δ-unsaturated carbonyls was developed. A mechanism involving bromopalladation of alkyne, followed by insertion of allylic alcohol and allylic hydrogen shift, is proposed. The shift of allylic hydrogen is the rate-limiting step in this reaction