Expanding the Horizons of Suzuki Reactions: Pd‐PEPPSI–Mediated Traditional and Decarbonylative Couplings With Diverse Assure Analogues

We have developed a highly efficient, ligand‐free Suzuki–Miyaura cross‐coupling protocol employing our lab‐prepared air and moisture‐stable Pd‐PEPPSI catalysts. The reaction of ethyl 2‐{4‐[(6‐chloroquinoxalin‐2‐yl)oxy]phenoxy}propionate (Assure) with various boronic acids afforded both traditional and decarbonylative coupling products in high yields. The catalyst's steric influence was assessed computationally using %Vbur calculations. The decarbonylative coupling pathway proved more efficient than the traditional Suzuki–Miyaura coupling under these conditions. Additionally, regioselectivity studies have been conducted on a variety of Assure analogues. This method excels in efficiency, requiring minimal catalyst, moderate temperatures, and rapid reaction completion.