Published August 30, 2021
| Version v1
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C-F bond activation under transition-metal-free conditions
- 1. Leibniz Institute for Catalysis
- 2. Fuzhou University
- 3. Dalian National Laboratory for Clean Energy
- 4. Dalian Institute of Chemical Physics
- 5. Chinese Academy of Sciences
Description
Abstract The unique properties of fluorine-containing organic compounds make fluorine substitution attractive for the development of pharmaceuticals and various specialty materials, which have inspired the evolution of diverse C-F bond activation techniques. Although many advances have been made in functionalizations of activated C-F bonds utilizing transition metal complexes, there are fewer approaches available for nonactivated C-F bonds due to the difficulty in oxidative addition of transition metals to the inert C-F bonds. In this regard, using Lewis acid to abstract the fluoride and light/radical initiator to generate the radical intermediate have emerged as powerful tools for activating those inert C-F bonds. Meanwhile, these transition-metal-free processes are greener, economical, and for the pharmaceutical industry, without heavy metal residues. This review provides an overview of recent C-F bond activations and functionalizations under transition-metal-free conditions. The key mechanisms involved are demonstrated and discussed in detail. Finally, a brief discussion on the existing limitations of this field and our perspective are presented.
Translated Descriptions
⚠️
This is an automatic machine translation with an accuracy of 90-95%
Translated Description (Arabic)
الخلاصة الخصائص الفريدة للمركبات العضوية المحتوية على الفلور تجعل استبدال الفلور جذابًا لتطوير المستحضرات الصيدلانية والمواد المتخصصة المختلفة، والتي ألهمت تطور تقنيات تنشيط روابط CF المتنوعة. على الرغم من إحراز العديد من التقدم في تفعيل روابط C - F المنشطة باستخدام المجمعات المعدنية الانتقالية، إلا أن هناك عددًا أقل من الأساليب المتاحة لروابط C - F غير المنشطة بسبب صعوبة الإضافة المؤكسدة للمعادن الانتقالية إلى روابط C - F الخاملة. في هذا الصدد، برز استخدام حمض لويس لتجريد الفلورايد والبادئ الخفيف/الجذري لتوليد الوسيط الجذري كأدوات قوية لتنشيط روابط C - F الخاملة هذه. وفي الوقت نفسه، فإن هذه العمليات الخالية من المعادن الانتقالية أكثر اخضرارًا واقتصادية ولصناعة المستحضرات الصيدلانية، بدون بقايا المعادن الثقيلة. تقدم هذه المراجعة نظرة عامة على التنشيط والوظائف الأخيرة لسندات C - F في ظل ظروف خالية من المعادن الانتقالية. يتم عرض الآليات الرئيسية المعنية ومناقشتها بالتفصيل. أخيرًا، يتم تقديم مناقشة موجزة حول القيود الحالية لهذا المجال ومنظورنا.Translated Description (French)
Résumé Les propriétés uniques des composés organiques contenant du fluor rendent la substitution du fluor attrayante pour le développement de produits pharmaceutiques et de divers matériaux spécialisés, qui ont inspiré l'évolution de diverses techniques d'activation des liaisons C-F. Bien que de nombreux progrès aient été réalisés dans les fonctionnalisations des liaisons C-F activées utilisant des complexes de métaux de transition, il existe moins d'approches disponibles pour les liaisons C-F non activées en raison de la difficulté d'addition oxydante des métaux de transition aux liaisons C-F inertes. À cet égard, l'utilisation de l'acide de Lewis pour extraire le fluorure et l'initiateur de lumière/radical pour générer l'intermédiaire radicalaire sont apparus comme des outils puissants pour activer ces liaisons C-F inertes. Pendant ce temps, ces procédés sans métaux de transition sont plus écologiques, économiques et pour l'industrie pharmaceutique, sans résidus de métaux lourds. Cette revue donne un aperçu des activations et des fonctionnalisations récentes des liaisons C-F dans des conditions sans métaux de transition. Les mécanismes clés impliqués sont démontrés et discutés en détail. Enfin, une brève discussion sur les limites existantes de ce domaine et notre point de vue sont présentés.Translated Description (Spanish)
Resumen Las propiedades únicas de los compuestos orgánicos que contienen flúor hacen que la sustitución del flúor sea atractiva para el desarrollo de productos farmacéuticos y diversos materiales especializados, que han inspirado la evolución de diversas técnicas de activación de enlaces C-F. Aunque se han realizado muchos avances en las funcionalizaciones de los enlaces C-F activados utilizando complejos de metales de transición, hay menos enfoques disponibles para los enlaces C-F no activados debido a la dificultad en la adición oxidativa de metales de transición a los enlaces C-F inertes. En este sentido, el uso de ácido de Lewis para abstraer el fluoruro y el iniciador de luz/radical para generar el radical intermedio han surgido como herramientas poderosas para activar esos enlaces C-F inertes. Mientras tanto, estos procesos sin metales de transición son más ecológicos, económicos y para la industria farmacéutica, sin residuos de metales pesados. Esta revisión proporciona una descripción general de las activaciones y funcionalizaciones recientes de los bonos C-F en condiciones libres de metales de transición. Los mecanismos clave involucrados se demuestran y discuten en detalle. Finalmente, se presenta una breve discusión sobre las limitaciones existentes en este campo y nuestra perspectiva.Files
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Additional details
Additional titles
- Translated title (Arabic)
- تفعيل السندات C - F في ظل الظروف الانتقالية الخالية من المعادن
- Translated title (French)
- Activation de la liaison C-F dans des conditions sans métal de transition
- Translated title (Spanish)
- Activación del enlace C-F en condiciones libres de metales de transición
Identifiers
- Other
- https://openalex.org/W3198565643
- DOI
- 10.1007/s11426-021-1040-2
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