Oxyarylations of alkenes represent a powerful tool to build new organic scaffolds from simple and cheap substrates. Although 1,2-oxyarylation of alkenes traditionally required exogenous oxidants,1,2 the very recent synthesis of gold catalysts, bearing a chelating (C^N) NHeterocyclic Carbene (NHC) ligand, allowed to react the alkene directly with an alcohol and an aryl iodine (Scheme 1).3 Herein, we report a DFT study on the whole catalytic cycle of 1,2-oxyarylation of ethylene in the presence of NHC-Au catalyst 13 (Scheme 2) with the intent to identify the rate determining steps. The computational study shows how the presence of a donor on the NHC is able to stabilize Au(III) species and how electronic and steric modifications of the ligand (2 and 3 in Scheme 2) can affect the rate determining step barriers. (1) Zhang, G.; Cui, L.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 1474–1475. (2) Harper, M.J.; Emmett, E.J.; Bower, J.F.; Russell, C. A. J. Am. Chem. Soc. 2017, 139, 12386−12389. (3) Scott. S.C; Cadge, J.A.; Boden, G.K.; Bower, J.F.; Russell, C.A. Angew. Chem. Int. Ed. 2023, 62, e202301526.
Steric and Electronic Properties of NHC ligands for Gold(I/III) catalyzed Oxyarylation of Ethylene: A Computational Study
Costabile Chiara
;Galdi Gaetano
2024
Abstract
Oxyarylations of alkenes represent a powerful tool to build new organic scaffolds from simple and cheap substrates. Although 1,2-oxyarylation of alkenes traditionally required exogenous oxidants,1,2 the very recent synthesis of gold catalysts, bearing a chelating (C^N) NHeterocyclic Carbene (NHC) ligand, allowed to react the alkene directly with an alcohol and an aryl iodine (Scheme 1).3 Herein, we report a DFT study on the whole catalytic cycle of 1,2-oxyarylation of ethylene in the presence of NHC-Au catalyst 13 (Scheme 2) with the intent to identify the rate determining steps. The computational study shows how the presence of a donor on the NHC is able to stabilize Au(III) species and how electronic and steric modifications of the ligand (2 and 3 in Scheme 2) can affect the rate determining step barriers. (1) Zhang, G.; Cui, L.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 1474–1475. (2) Harper, M.J.; Emmett, E.J.; Bower, J.F.; Russell, C. A. J. Am. Chem. Soc. 2017, 139, 12386−12389. (3) Scott. S.C; Cadge, J.A.; Boden, G.K.; Bower, J.F.; Russell, C.A. Angew. Chem. Int. Ed. 2023, 62, e202301526.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
