INFIQC   05475
INSTITUTO DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Unidad Ejecutora - UE
capítulos de libros
Título:
Homolytic Aromatic Substitution
Autor/es:
ROSSI, R. A.; MARÍA E. BUDÉN; JAVIER F. GUASTAVINO
Libro:
Arene Chemistry: Reaction Mechanisms and Methods for Aromatic Compounds
Editorial:
WILEY
Referencias:
Año: 2015; p. 219 - 242
Resumen:
Homolytic Aromatic Substitution (HAS) encompasses a wide range of synthetic transformations based on inter- and intramolecular additions of radicals to arenes. This chapter is intended to provide a description of important aspects and recent advances of these reactions including the principal mechanisms, and the synthetic protocols used. This is not intended to be exhaustive, and the reader is referred to reviews for complete information. An overview of selected examples are shown, which can be used as guides for a planned transformation. The chapter has been organized according to the different routes to generate the intermediate radicals. The first one involves the use of peroxides, persistent radicals or free radical initiator with tin hydrides, and silanes. In the second route, the radicals are formed by homolysis (thermolysis and photolysis). Finally, the third route involves redox reactions. In such processes, an electron is transferred to a molecule possessing paired electrons, thereby generating a radical anion; the fragmentation of this latter species leads to a radical and the anion. Another way for redox process involves directed oxidation (or reduction) of an anion (or a cation) leading to the formation of a radical. Also we will discuss the base-promoted electron transfer to induced the HAS.