High-ThroughputEnabled Iridium-Catalyzed C–HBorylation Platform for Late-Stage Functionalization

In this work, we present a dedicated, high-throughput reaction optimization platform allowing for the rapid evaluation of regiodivergent C–H borylation protocols while minimizing the amount of starting material required. The workflow was applied to a diverse set of fragment-like compounds, pharmaceuticals, and agrochemicals, and its practicality was demonstrated by successfully isolating 36 derivatives of bioactive compounds. Leveraging the informer library approach, we provide a comprehensive, side-by-side comparison of catalytic methods, revealing insights into the strengths, limitations, and versatility of each borylation protocol. Surprising reactivity patterns, effectiveness of ligand-free C–H borylation, and the utility of previously reported directed C–H borylation catalysts outside of their expected substrate scope have been noticed. This study highlights the potential of dedicated high-throughput optimization platforms to expand the practical utility of late-stage functionalization protocols for pharmaceutical and agrochemical research.