Production of new carbon-heteroatom bonds induced by visible light

• Autores: Jorge Carlos Herrera Luna
• Directores de la Tesis: Susana Encinas Perea (dir. tes.), Raúl Pérez Ruiz (dir. tes.), María Consuelo Jiménez Molero (dir. tes.)
• Lectura: En la Universitat Politècnica de València ( España ) en 2022
• Idioma: español
• Tribunal Calificador de la Tesis: Rosario Fernández Fernández (presid.), Félix Sancenón Galarza (secret.), Gustavo Fernandez Huertas (voc.)
• Programa de doctorado: Programa de Doctorado en Química por la Universitat de València (Estudi General) y la Universitat Politècnica de València
• Materias:
  • Química
    • Química orgánica
• Enlaces
  • Tesis en acceso abierto en: RiuNet
• Resumen

  • This thesis doctoral describes novel, simple, and rapid methodologies using visible light to produce compounds with new C-heteroatom bonds such as C-B, C-P and C-S that represent valuable scaffolds in modern organic synthesis. The employment of visible light as energy source highlights the concepts of green and sustainable chemistry considering its mild, safe, and eco-friendly advantages. On the other hand, spatially nanoreactors such as viscoelastic gel networks by 'bottom-up' approaches to improve different processes in comparison to solution, in terms of kinetics, selectivity or processability have been also developed.

    Thus, Chapter 3 describes a novel, straightforward, and fast procedure to produce boron-containing thiophenes employing visible light in anaerobic solution. Interestingly, the process does not require the use of any external photocatalyst. This study has been extended to the borylation of commercially available heteroarene halides under aerobic conditions in an easy-to-use gel nanoreactor (Chapter 4). The gel network provides an adequate stabilizing microenvironment to support wide substrate scope, including furan, thiophene, selenophene, and pyrrole boronate esters.

    Chapter 5 focus on a new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes using dichromatic photoredox catalysis in a gel-based nanoreactor. The methodology, which operates by a consecutive photoinduced electron transfer (ConPET) mechanism, has been successfully applied to the straightforward and clean synthesis of a number of different heteroarene (furan, thiophene, selenophene, pyrrole, oxazole, or thioxazole) phosphonates, extending to the late-stage phosphonylation of the anticoagulant rivaroxaban.

    Lastly, regarding the construction of new C-S bonds, Chapter 6 shows a simple and effective metal-free thiolation of commercial heteroarene halides using visible light. The experimental results are consistent with the reaction taking place from an electron donor-acceptor (EDA) complex between an alkylamine and the heteroarene halide. Mechanistic aspects of the whole process have been demonstrated by spectroscopic measurements whereas the strength of this novel method has been proven by gram-scale experiment and late-stage derivatization.