Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
Gold-catalyzed redox transformations via Au(I)/Au(III) cycles offer efficient oxidative addition and reductive elimination under mild, oxidant-free conditions. Recent studies highlight the role of hemilabile mesoionic carbene (MIC) ligands in stabilizing key intermediates. Using DFT, we investigated...
| Autores: | , , , |
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| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2025 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositório: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/27220 |
| Acesso em linha: | http://hdl.handle.net/10256/27220 |
| Access Level: | Acceso aberto |
| Palavra-chave: | Anions Catalitzadors Catalysts Lligands Ligands Reaccions químiques orgàniques -- Mecanismes Organic reaction mechanisms Reaccions d'addició Addition reactions |
| Resumo: | Gold-catalyzed redox transformations via Au(I)/Au(III) cycles offer efficient oxidative addition and reductive elimination under mild, oxidant-free conditions. Recent studies highlight the role of hemilabile mesoionic carbene (MIC) ligands in stabilizing key intermediates. Using DFT, we investigated the mechanism of the arylation-lactonization of γ-alkenoic acids, revealing two viable pathways, cis and trans, each with distinct rate-determining steps. While the trans pathway avoids decomposition of the catalyst, its lactonization step is hindered by a high barrier. In contrast, the cis pathway features competing productive and decomposition routes. By correlating computed activation barriers with experimental yields, we built statistically significant multivariable models (R2 = 0.919), enabling the prediction of product yields across various substituted aryl iodides. These models revealed clear electronic and steric trends. Additionally, ligand modifications suggest that trans-selective oxidative addition can be improved through steric tuning with the trans effect also influencing selectivity. Overall, this study provides valuable design principles for future gold-catalyzed redox processes |
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