NH2-Directed C-H Alkenylation of 2-Vinylanilines with Vinylbenziodoxolones.

The first directing-group-mediated C-H alkenylation with alkenyl-λ3-iodanes as electrophilic alkene-transfer reagents has been developed. The application of free aromatic amines as challenging but synthetically valuable directing groups in combination with an IrIII catalyst enabled the synthesis of highly desirable 1,3-dienes in excellent yields of up to 98% with high to perfect (Z,E) stereoselectivity. A broad substrate scope and further synthetic modifications are demonstrated.