Palladium(II)/Lewis Acid-Catalyzed Oxidative Olefination/Annulation of <i>N</i>-Methoxybenzamides: Identifying the Active Intermediates through NMR Characterizations

Abstract

Although Pd(II)-catalyzed C-H activation in arenes has been widely successful in organic synthesis with many palladacycle compounds isolated as the intermediates in ligand-directed C-H activation, direct identification of the reaction intermediates such as the π-complex prior to the C-H activation is still not successful because of their instability. In the present study, we introduce a Pd(II)/LA (LA: Lewis acid)-catalyzed oxidative olefination/annulation reaction between <i>N</i>-methoxybenzamides and acrylates with oxygen as the oxidant source, in which two intermediates, including an unsymmetrical η⁶-complex and a palladacycle species without the proton releasing to the environment, were identified through NMR characterizations. The <i>in situ</i> formation of the heterobimetallic Pd(II)/LA species such as Pd(II)/Sc(III) may have enhanced the electrophilic properties of the Pd²⁺ cation, thus improving the stability of the π-complex, herein, an unsymmetrical η⁶-complex, and improving its catalytic efficiency. The observed insensitive electronic effect preferred the concerted metalation-deprotonation (CMD) mechanism for this C-H activation, and the detected palladacycle intermediate without the proton releasing to the environment offered an experimental clue to support the proposed CMD mechanism.