Oxyarylation of alkenes is a potent method for building novel organic frameworks using highly abundant and synthetic versatile feedstock chemicals. While the traditional catalytic processes required strong external oxidants1, recently N-Heterocyclic Carbene (NHC) gold catalysts, as complex 1 in Scheme 1, showed to promote the 1,2-difunctionalisation of widely available raw materials such as ethylene and propylene using a broad range of aryl iodides and alcohols (Scheme 1).2 The highly tunable nature of NHC ligands disclose the possibility to design and develop new and more efficient catalysts. The herein reported DFT study reveals how the inclusion of a different donating side-arm on the NHC, but also steric and electronic modifications of the ligand, can influence the energies of the rate-determining steps. Contextual synthesis of hemilabile NHC-Au(I) complexes (2 in Scheme 2) is ongoing with the aim of performing an experimental evaluation of their catalytic behaviour. References (1) Zheng, Z.; Ma, X.; Cheng, X.; Zhao, K.; Gutman, K.; Li, T.; Zhang, L. Chem. Rev. 2021, 121 (14), 8979–9038. (2) Scott, S. C.; Cadge, J. A.; Boden, G. K.; Bower, J. F.; Russell, C. A. Angew. Chem. Int. Ed. 2023, 62 (23), e202301526.
Mechanistic insights into the 1,2-oxyarylation of ethylene promoted by NHC-Gold(I/III) catalysts
Gaetano Galdi;Assunta D’Amato;Fabia Grisi;Pasquale Longo;Chiara Costabile
2024-01-01
Abstract
Oxyarylation of alkenes is a potent method for building novel organic frameworks using highly abundant and synthetic versatile feedstock chemicals. While the traditional catalytic processes required strong external oxidants1, recently N-Heterocyclic Carbene (NHC) gold catalysts, as complex 1 in Scheme 1, showed to promote the 1,2-difunctionalisation of widely available raw materials such as ethylene and propylene using a broad range of aryl iodides and alcohols (Scheme 1).2 The highly tunable nature of NHC ligands disclose the possibility to design and develop new and more efficient catalysts. The herein reported DFT study reveals how the inclusion of a different donating side-arm on the NHC, but also steric and electronic modifications of the ligand, can influence the energies of the rate-determining steps. Contextual synthesis of hemilabile NHC-Au(I) complexes (2 in Scheme 2) is ongoing with the aim of performing an experimental evaluation of their catalytic behaviour. References (1) Zheng, Z.; Ma, X.; Cheng, X.; Zhao, K.; Gutman, K.; Li, T.; Zhang, L. Chem. Rev. 2021, 121 (14), 8979–9038. (2) Scott, S. C.; Cadge, J. A.; Boden, G. K.; Bower, J. F.; Russell, C. A. Angew. Chem. Int. Ed. 2023, 62 (23), e202301526.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
