Distortion/Interaction Analysis Reveals the Origins of Selectivities in Iridium-Catalyzed C-H Borylation of Substituted Arenes and 5-Membered Heterocycles.

The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H o...

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Detalles Bibliográficos
Publicado en:	Journal of the American Chemical Society Vol. 136; no. 12; pp. 4575 - 4584
Autores principales:	Green, Aaron G., Peng Liu, Merlic, Craig A., Houk, K. N.
Formato:	Artículo
Publicado:	American Chemical Society 3/26/2014
Materias:	Iridium catalysts Density functional theory Carbon-hydrogen bonds Heteroarenes Aromatic compounds Transition state theory (Chemistry) Oxidative addition Regioselectivity (Chemistry)
Acceso en línea:	Ver este registro en EBSCOhost

Descripción
Sumario:	The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir-C bond. Consequently, the regioselectivity is mainly controlled by differences in the interaction energies between the iridium catalyst and arene carbon.