The pharmaceutical and chemical industries heavily rely on the production of N-containing compounds, as these molecules serve as scaffolds for the synthesis of both fine chemicals and polymers of interest. The hydroamination reaction can be hailed as a paradigm of a contemporary, sustainable, catalytically promoted chemical process, since it can form C-N bonds by adding amines to multiple carbon bonds with a 100% atom economy.1 By reducing the high energy barriers connected to alkyne activation, use of metal complexes can facilitate this process; lately, gold(I) N-heterocyclic (NHC) complexes were demonstrated to be promising in this regard.2 Herein, we present a library of gold(I)-NHC complexes which were identified as promising catalysts for regioselective Markovnikov addition of aromatic and aliphatic alkynes to anilines, with high yields.3 Accurate catalyst’ design, experimental reaction scope and computational mechanistic insight will be presented, by means of which the nonmonotonic impact of substrate substituents on the reaction course was elucidated. References (1) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795–3892. (2) Mariconda, A.; Sirignano, M.; Troiano, R.; Russo, S.; Longo, P. Catalysts 2022, 12(8), 836. (3) Sirignano, M.; D’Amato, A.; Costabile, C.; Mariconda, A.; Crispini, A.; Scarpelli, F.; Longo, P. Front. Chem. 2023, 11, 1260726.
Alkyne Hydroamination Promoted by NHC-Gold(I) Complexes: Activity and Mechanistic Insight
Assunta D’Amato;Marco Sirignano;Chiara Costabile
;Pasquale Longo
2024-01-01
Abstract
The pharmaceutical and chemical industries heavily rely on the production of N-containing compounds, as these molecules serve as scaffolds for the synthesis of both fine chemicals and polymers of interest. The hydroamination reaction can be hailed as a paradigm of a contemporary, sustainable, catalytically promoted chemical process, since it can form C-N bonds by adding amines to multiple carbon bonds with a 100% atom economy.1 By reducing the high energy barriers connected to alkyne activation, use of metal complexes can facilitate this process; lately, gold(I) N-heterocyclic (NHC) complexes were demonstrated to be promising in this regard.2 Herein, we present a library of gold(I)-NHC complexes which were identified as promising catalysts for regioselective Markovnikov addition of aromatic and aliphatic alkynes to anilines, with high yields.3 Accurate catalyst’ design, experimental reaction scope and computational mechanistic insight will be presented, by means of which the nonmonotonic impact of substrate substituents on the reaction course was elucidated. References (1) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795–3892. (2) Mariconda, A.; Sirignano, M.; Troiano, R.; Russo, S.; Longo, P. Catalysts 2022, 12(8), 836. (3) Sirignano, M.; D’Amato, A.; Costabile, C.; Mariconda, A.; Crispini, A.; Scarpelli, F.; Longo, P. Front. Chem. 2023, 11, 1260726.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
