Rhodium(III)‐Catalyzed Direct CH Olefination of Arenes with Aliphatic Olefins

A rhodium(III)‐catalyzed direct ortho CH bond olefination of arenes, including but not limited to benzamides, arylpyridines and indoles, with a variety of unactivated aliphatic olefins has been developed. In the presence of catalytic amounts of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer {[Cp*RhCl 2 ] 2 }, copper(II) acetate monohydrate [Cu(OAc) 2 ⋅H 2 O] and silver hexafluoroantimonate(V) (AgSbF 6 ), the coupling reaction occurred efficiently to afford the ortho ‐olefinated linear products in good to excellent yields with high regio‐ and stereoselectivities, and a range of functional groups in both coupling partners is compatible with the reaction conditions. This protocol relies on the use of directing groups, and the addition of AgSbF 6 as additive is crucial for the catalysis. This new method expands the scope of rhodium(III)‐catalyzed direct CH bond olefination of arenes, and provides a rapid access to useful linear arylation products of unactivated olefins.