Rhenium-CatalyzedC(sp²)–H Silylalkenylationof Arenes: An Anti-Markovnikov Linchpin Strategy

Re-catalyzed highly regio- and stereoselective <i>o</i>-C­(sp²)–H silylalkenylation of arenes is reported using a directing group approach under ligand-, additive-, and base-free conditions. A series of imine directing groups (DGs) have been exploited on aromatic aldehydes to overcome <i>de novo</i> synthesis. This unique protocol allows us to access <i>o</i>-C–H activation of various heterocyclic moieties, including <i>N</i>-aryl 2-pyridones and arylpyridines. Sequential difunctionalization experiments have been performed. A series of mechanistic experiments have been carried out to gain mechanistic insight.