Kinetic Study of Carbophilic Lewis Acid Catalyzed Oxyboration and the Noninnocent Role of Sodium Chloride

In the present study, the oxyboration reaction catalyzed by IPrAuTFA in the presence and absence of NaTFA has been examined with kinetic studies, mass spectrometry, and 1H NMR and 11B NMR spectroscopy. Data from monitoring the reactions over the temperature range from 30 to 70 °C, the catalyst range from 1.3 to 7.5 mol %, and the NaTFA additive range from 2.5 to 30 mol % suggests a mechanism that involves rate-determining catalyst generation. Data from additive studies that replaced NaTFA with NaBARF (BARF = tetrakis­[3,5-bis­(trifluoromethyl)­phenyl]­borate) or Bu4NTFA as an alternative additive suggest that catalyst quenching from residual NaCl remaining from a one-pot substrate synthesis/reaction method is the cause of this effect, despite the low solubility of this NaCl byproduct in toluene. Material produced through an alternative, sodium chloride-free substrate synthesis exhibited faster reaction rates, consistent with a change in rate-determining step that depended on the substrate synthesis route.