High‐Throughput Experimentation‐Assisted Optimization of the Suzuki–Miyaura Coupling Using Palladium– N ‐Heterocyclic Carbene Precatalysts

High‐throughput experimentation (HTE) was employed to optimize the Suzuki–Miyaura coupling of electronically challenging substrates using a series of N ‐heterocyclic carbene–palladium precatalysts. The screening of 768 conditions revealed that sulfide‐based and PEPPSI‐type Pd‐NHC complexes showed highest activity, with cesium carbonate identified as the most effective base. Further optimization showed that careful adjustment of base and boronic acid loading was essential to minimize side‐product formation, while the addition of water accelerated the process and enabled efficient catalysis at 1 mol % Pd loading. The resulting conditions delivered >98% yield within 1 h, demonstrating how the integration of HTE and targeted optimization can permit the rapid identification of robust and sustainable protocols for cross‐coupling chemistry.