Rhenium-Catalyzed C(sp²)-H Silylalkenylation of Arenes: An Anti-Markovnikov Linchpin Strategy

Re-catalyzed highly regio- and stereoselective o-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 de novo synthesis. This unique protocol allows us to access o-C-H activation of various heterocyclic moieties, including N-aryl 2-pyridones and arylpyridines. Sequential difunctionalization experiments have been performed. A series of mechanistic experiments have been carried out to gain mechanistic insight.