The synthesis of propargylamines by traditional methods is limited by several drawbacks such as anhydrous conditions, low temperatures and by-products. A3-coupling reactions (aldehydes, amines, and alkynes), that involve a catalytic amount of metal complexes, have been recently recognized as a powerful alternative for the synthesis of these important scaffolds. In this paper, four new silver and gold complexes (3a,4a,3band4b), bearing N-heterocyclic carbene (NHC) ligands, were tested in A3-coupling reactions, combining the use of harmless metals as catalysts with sustainable reaction conditions (neat conditions or water as solvent). NHC silver(i) and gold(i) complexes were synthesized and characterized by1H and13C NMR spectroscopy, ESI-MS and elemental analysis. The molecular structure of the NHC gold(i) complex4bwas determined by single crystal X-ray diffraction. A comparison of the catalytic behavior in A3-coupling reactions among the synthesized complexes disclosed the higher efficiency of gold catalysts. Computational studies shed light on species possibly involved in the catalytic mechanism.
A green approach for A3-coupling reactions: an experimental and theoretical study on NHC silver and gold catalysts
Crispini A.;Scarpelli F.;
2021-01-01
Abstract
The synthesis of propargylamines by traditional methods is limited by several drawbacks such as anhydrous conditions, low temperatures and by-products. A3-coupling reactions (aldehydes, amines, and alkynes), that involve a catalytic amount of metal complexes, have been recently recognized as a powerful alternative for the synthesis of these important scaffolds. In this paper, four new silver and gold complexes (3a,4a,3band4b), bearing N-heterocyclic carbene (NHC) ligands, were tested in A3-coupling reactions, combining the use of harmless metals as catalysts with sustainable reaction conditions (neat conditions or water as solvent). NHC silver(i) and gold(i) complexes were synthesized and characterized by1H and13C NMR spectroscopy, ESI-MS and elemental analysis. The molecular structure of the NHC gold(i) complex4bwas determined by single crystal X-ray diffraction. A comparison of the catalytic behavior in A3-coupling reactions among the synthesized complexes disclosed the higher efficiency of gold catalysts. Computational studies shed light on species possibly involved in the catalytic mechanism.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
