Catalyst Control in Positional-Selective C–H Alkenylation of Isoxazoles and a Ruthenium-Mediated Assembly of Trisubstituted Pyrroles

High levels of catalyst control are demonstrated in determining the positional selectivity in C–H alkenylation of isoxazoles. A cationic rhodium-mediated, strong-directing group promotes C(sp2)-H activation at the proximal aryl ring whereas, the palladium-mediated electrophilic metallation leads to the C(sp2)-H activation at the distal position of the directing group. Synthetic elaboration of this C–H alkenylation product via ruthenium and copper co-catalysis leads to an efficient method for the assembly of densely substituted pyrroles.