Silver-catalysed intramolecular hydroamination of alkynes with trichloroacetimidates

Abstract

Silver(I) complexes catalyse the intramolecular addition of trichloroacetimidates to alkynes. In the absence of a ligand, the selectivity of the reaction is dependent upon the nature of the counter-anion and solvent. The introduction of non-chelating nitrogeneous ligands suppresses competitive Brønsted acid catalysis, improving the yield and selectivity of the reaction.

Silver-catalysed reactions of alkynes: recent advances

“…146 Methylene-substituted heterocycles 187 were obtained through 5-and 6-exo-dig annulations with 29-99% yields and (Z)-selectivity. 146 Methylene-substituted heterocycles 187 were obtained through 5-and 6-exo-dig annulations with 29-99% yields and (Z)-selectivity.…”

Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

“…In this case, the bond energy decomposition analysis also showed a good correlation between the magnetic shielding on the P atom and the orbital energy contribution, E π , see Figure 10. recently, see Chart 7 [80,81]. In contrast to Cu and Au, only a few Ag-NHC complexes have been experimentally investigated, due to the easier 'decomposition' reaction of ligand exchange yielding a bis-ligated complex [82].…”

Synthesis, Structure and Catalytic Activity of NHC–AgI Carboxylate Complexes

“…More recently, this was extended to the intramolecular addition of NÀHa nd OÀHb onds to alkynes to form substituted oxazolines at ambientc onditions (Scheme 1). [16,25,26] Catalytic turnoversw ere found to be very responsive to the electronic characteristics of the pyridine ligands. Notably,N ÀHa dditions were promoted by electron-deficient pyridyl ligands (Scheme 1a), while the opposite trend was observed for OÀH additions (Scheme 1b).…”

“…Our group has an ongoing interest in the catalytic activity of cheaper coinage metal (Cu and Ag) catalysts for the heterofunctionalisation of unsaturated carbon–carbon bonds. More recently, this was extended to the intramolecular addition of N−H and O−H bonds to alkynes to form substituted oxazolines at ambient conditions (Scheme ) . Catalytic turnovers were found to be very responsive to the electronic characteristics of the pyridine ligands.…”