A Radical Strategy to the Synthesis of Bicyclo[1.1.1]pentyl C−Glycosides

Aryl C-glycosides are widely represented in natural products and pharmaceuticals, yet their saturated analogs remain elusive. Here, we address this challenge with a diastereoselective radical strategy for the efficient synthesis of bicyclopentyl C-glycosides via addition of glycosyl radicals to [1.1.1]propellane. Experimental and DFT studies support a radical chain mechanism under kinetic control. The protocol is practical, mild, and general, and amenable to scalable synthesis in continuous flow. Products manipulations allow easy access to a variety of three-dimensional aryl C-glycosides analogs.