Visible-Light Radical–Radical Coupling vs. Radical Addition: Disentangling a Mechanistic Knot
| العنوان: | Visible-Light Radical–Radical Coupling vs. Radical Addition: Disentangling a Mechanistic Knot |
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| المؤلفون: | Ricardo I. Rodríguez, José Alemán, Leonardo Mollari, Sergio Díaz-Tendero, Fernando Aguilar-Galindo |
| المصدر: | Catalysts Volume 11 Issue 8 Catalysts, Vol 11, Iss 922, p 922 (2021) |
| بيانات النشر: | Multidisciplinary Digital Publishing Institute, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | Imine, asymmetric synthesis, TP1-1185, radical–radical coupling, 010402 general chemistry, 01 natural sciences, Quantum chemistry, Catalysis, chemistry.chemical_compound, Computational chemistry, Physical and Theoretical Chemistry, QD1-999, Heterocyclic derivatives, radical addition, density functional theory, Process strategy, 010405 organic chemistry, Chemical technology, Enantioselective synthesis, pyrroline derivative, 0104 chemical sciences, Chemistry, chemistry, Coupling (computer programming), Mechanism (philosophy), photocatalysis, Knot (mathematics) |
| الوصف: | A highly enantioselective protocol has been recently described as allowing the synthesis of five-membered cyclic imines harnessing the selective generation of a β-Csp3-centered radical of acyl heterocyclic derivatives and its subsequent interaction with diverse NH-ketimines. The overall transformation represents a novel cascade process strategy crafted by individual well-known steps however, the construction of the new C-C bond highlights a crucial knot from a mechanistically perspective. We believe that the full understanding of this enigmatic step may enrich the current literature and expand latent future ideas. Therefore, a detailed mechanistic study of the protocol has been conducted. Here, we provide theoretical insight into the mechanism using quantum chemistry calculations. Two possible pathways have been investigated: (a) imine reduction followed by radical–radical coupling and (b) radical addition followed by product reduction. In addition, investigations to unveil the origin behind the enantioselectivity of the 1-pyrroline derivatives have been conducted as well. |
| وصف الملف: | application/pdf |
| اللغة: | English |
| تدمد: | 2073-4344 |
| DOI: | 10.3390/catal11080922 |
| الوصول الحر: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::629bcd524ee582345c1b453816af0d23Test |
| حقوق: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....629bcd524ee582345c1b453816af0d23 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 20734344 |
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| DOI: | 10.3390/catal11080922 |