Palladium-catalyzed cross-coupling for carbon-element bond formation continues to be one of the most important methods in synthetic chemistry. Despite decades of research, discovering an optimal catalyst system for a known or new transformation is still experimentally challenging, requiring a combination of knowledge, intuition, perseverence, and (often) luck. High-throughput experimentation (HTE) is a powerful approach to expand the scope of accessible reaction space during screening and discovery. Our research group is developing new tools to enable HTE, as well as using HTE to discovery and develop new transformations. In an effort to create a universal palladium source for reliable in situ precatalyst formation during HTE screening, we have developed an easily prepared, stable, and versatile palladium(0) source - DMPDAB-Pd-MAH - that undergoes rapid phosphine metallation at room temperature even with the most sterically-hindered ligands. Our preliminary studies of this complex, including applications in high-throughput experimentation, will be presented. In pursuit of new reaction chemistries with Pd-catalysis, we are leveraging HTE to develop a series of transformations that utilize carboxylate-based electrophiles for cross-coupling and related reactions. We recently disclosed our initial efforts in this area, involving the coupling of aryl boronic acids with alkenyl carboxylates (Angew. Chem. Int. Ed. 2020, 59, 17277-17281). Our efforts toward expanding this class of coupling reaction will also be presented.

High-throughput organopalladium chemistry: New tools and new reactions

ACS Spring Meeting 2021

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