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Published on: June 23, 2019
Thorpe-Ingold Effect in Branch-Selective Alkylation of Unactivated Aryl Fluorides
Matthew J O'Neill1, Tim Riesebeck1, Josep Cornella1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
Abstract:
Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe-Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C-C coupling event. This protocol is characterized by mild reaction conditions, robustness, and simplicity. Both electron-rich and electron-deficient aryl fluorides are suitable candidates in this transformation. Equally amenable are a variety of heterocycles, permitting the coupling without over alkylation at the electrophilic sites.
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