Cross dehydrogenative coupling is a powerful means to form carbon-carbon bonds. This transformation avoids the use of pre-functionalized starting materials like organometallic reagents and organic halides contributing to overall efficiency. However, these reactions are predominantly catalyzed by homogeneous catalysts. Herein, we describe a novel benzylation of sterically challenging tertiary carbon centers with a heterogeneous palladium catalyst and readily available toluene derivatives. The reaction condition can be applied to various substrates ranges from azlactone to fluorene with good to excellent yields. Mechanism studies suggest that the reaction is catalyzed by heterogeneous palladium particles rather than Pd(OAc)<sub>2</sub> inputs, which was confirmed by activity with commercially available Pd/C. Pd/C provided several advantages in terms of substrate scope and provides motifs that are found in various agrochemicals, materials and drug molecules. Furthermore, a detailed mechanistic study reveals a framework to allow the discovery of other new transformations with heterogeneous catalysts.

Heterogeneous palladium-catalyzed oxidative benzylation via benzylic C(sp3)-H activation

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.