Visible-light assisted adaptive migratory cross-electrophile coupling with D-glucose and aryl bromide

The selective catalytic strategies for C–O bond activation in saccharides have predominantly centered on predictable and straightforward synthetic logic, as these approaches enable the exclusive formation of new bonds at the original C–O bond sites. Herein, we report a configuration-matched adaptive migratory cross-electrophile coupling (XEC) protocol for D-glucose. This strategy features a tandem in situ conversion of both free and protected hydroxyl groups to bromides, followed by transition-metal-catalyzed cross-electrophile coupling. Notably, a series of alternative product isomers was obtained, distinct from those derived from the cleavage of C–O bonds at the original hydroxyl-bearing positions of glucose. Preliminary mechanistic investigations indicate that the inherent configuration of glucose and the flexible protecting groups facilitate the migratory process. Importantly, the addition of POP, TBAB, and BTMG plays a pivotal role in promoting this XEC transformation. A visible light-assisted migratory cross-electrophile coupling with D-glucose and aryl bromide was reported. A tandem in situ conversion of both free and protected hydroxyl groups to bromides, followed by transition-metal-catalyzed cross-electrophile coupling. And a series of alternative product isomers was obtained, distinct from those derived from the cleavage of C–O bonds at the original hydroxyl-bearing positions of glucose.