Carbonylative Suzuki–Miyaura Coupling of 1‐Iodoglycals Mediated by the N ‐Heterocyclic Carbene Catalyst PEPPSI: Preparation of C ‐Acyl Glycosides

Suzuki–Miyaura coupling has been widely explored, particularly in the development of pharmaceutically relevant structures. Its carbonylative variant enables the insertion of a CO bridge, granting access to a variety of bioactive biaryl ketone scaffolds. Herein, we describe a carbonylative Suzuki–Miyaura strategy for the preparation of a series of C ‐acyl glycosides, thereby expanding the chemical space for the development of new derivatives in glycochemistry. The reaction proceeds under Pyridine‐Enhanced Precatalyst Preparation, Stabilization, and Initiation (PEPPSI‐IPr) (1,3‐Bis(2,6‐Diisopropylphenyl)imidazol‐2‐ylidene(3‐chloropyridyl)palladium(II) dichloride) catalysis, employing Mo(CO) 6 as a solid CO source for the in situ generation of CO, which enables the selective formation of the carbonylated products. The desired compounds were obtained in synthetically useful yields (up to 84%).