Abstract The aerobic dehydrogenative Heck reaction (DHR) of heterocycles with styrenes was found to be more efficient in the absence of metallic co-oxidants. According to a study of the isotope effect, the C [BOND] H cleavage was the rate-determining step of the catalytic cycle. Electrospray ionization mass spectrometry, subsequent MS/MS, and high-resolution mass spectrometry were used to detect and characterize catalytic intermediates and ...