On the Mechanism of Halogen Atom Transfer from C−X Bonds to α‐Aminoalkyl Radicals: A Computational Study
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Universidad de La Rioja
info
ISSN: 1434-193X, 1099-0690
Año de publicación: 2022
Tipo: Artículo
beta Ver similares en nube de resultadosOtras publicaciones en: European Journal of Organic Chemistry
Objetivos de desarrollo sostenible
Resumen
Generation of carbon centered radicals from organic halides represents a powerful tool in modern organic chemistry, especially in the context of photoredox catalysis. However, activation of carbon–halogen bonds is usually promoted by toxic and hazardous tin reagents. Alternatively, α-aminoalkyl radicals have emerged as a cheap and efficient halogen atom transfer (XAT) reagents, although the activation mechanism is still underexplored with respect to hydrogen atom transfer (HAT) chemistry. Herein, we report a computational systematic evaluation of four different α-aminoalkyl radicals on the Halogen Atom Transfer (XAT) mechanism. We have evaluated up to 32 reactions, including two different types of substrates (Ph−X and Cy−X). This systematic study aims to provide a big picture on the key effects in this reactivity including the hybridization of carbon, the nature of the halogen, and the electronics/sterics of the α-aminoalkyl radical.
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