Ligand switchable site selectivity in C-H alkenylation of thiophenes by turnover-limiting step control

The origin of switchable site selectivity during Pd-catalysed C-H alkenylation of heteroarenes has been examined through More O'Ferrall-Jencks, isotope effect, and DFT computational analyses, which indicate substitution of ionic thioether for pyridine dative ligands induces a change from selectivity-determining C-H cleavage to C-C bond formation, respectively.