The catalytic activity of a series of ruthenium complexes lacking cyclopentadienyl ligands has been evaluated for the cycloaddition of terminal alkynes and azides to give selectively 1,4-disubstituted 1,2,3-triazoles. The complex RuH(η 2-BH 4)(CO)(PCy 3) 2 was found to be an effective catalyst for the cycloaddition reactions. In the presence of RuH(η 2-BH 4)(CO)(PCy 3) 2, primary and secondary azides reacted with a range of terminal alkynes containing various functionalities to selectively produce 1,4-disubstituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition appears to proceed via a Ru-acetylide species as the key intermediate, which undergoes formal cycloaddition with an azide to give a ruthenium triazolide complex. The 1,4-disubstituted 1,2,3-triazole product is generated by metathesis of the triazolide complex with a terminal alkyne. In support of the reaction mechanism, the acetylide complex Ru(C≡CCMe 3) 2(CO)(PPh 3) 3 reacts cleanly with benzyl azide to give a ruthenium triazolide complex, which reacts with excess tert-butylacetylene in the presence of PPh 3 to give 4-tert-butyl-1-benzyl-1,2,3-triazole and the diacetylide complex Ru(C≡CCMe 3) 2(CO)(PPh 3) 3. The mechanism is also supported by DFT calculations.
ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry