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

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• 作者：Aaron G. Green ; Peng Liu ; Craig A. Merlic ; K. N. Houk
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：March 26, 2014
• 年：2014
• 卷：136
• 期：12
• 页码：4575-4583
• 全文大小：429K
• 年卷期：v.136,no.12(March 26, 2014)
• ISSN：1520-5126

文摘

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鈥揌 oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir鈥揅 bond. Consequently, the regioselectivity is mainly controlled by differences in the interaction energies between the iridium catalyst and arene carbon.