C−H Activation and Palladium Migration within Biaryls under Heck Reaction Conditions

Abstract
[reaction: see text] Biaryl bromides such as 1 (R=NO(2), H, OMe) undergo the Heck reaction to give both the expected products 3 ("retention") as well as "crossover" products 4 derived from a migration of Pd and net transfer of reactivity from one aryl ring to the other. Under the conditions used, crossover is increasingly favored when electron-deficient arenes are involved. Crossover products derived from transfer onto the pyridine ring have also been observed.