A Study of the Scope and Regioselectivity of the Ruthenium-Catalyzed [3 + 2]-Cycloaddition of Azides with Internal Alkynes

[3 + 2]-Cycloadditions of alkyl azides with various unsymmetrical internal alkynes in the presence of Cp*RuCl(PPh₃)₂ as catalyst in refluxing benzene have been examined, leading to 1,4,5-trisubstituted-1,2,3-triazoles. Whereas alkyl phenyl and dialkyl acetylenes undergo cycloadditions to afford mixtures of regioisomeric 1,2,3-triazoles, acyl-substituted internal alkynes react with complete regioselectivity. In addition, propargyl alcohols and propargyl amines were found to react with azides to afford single regioisomeric products.