Ag(I)‐Driven Stereoselective <i>C</i> −3 Glycosylation of Indoles: An Access to <i>C</i> ‐Glycosides and <i>N</i> ‐Orthoester Type Glycohybrids

Herein, we present an efficient one‐pot method for the stereoselective synthesis of 3‐indolyl‐ C ‐glycosides as glycohybrids. This process involves coupling of easily accessible various glycosyl bromides, including monosaccharides and disaccharides, with a diverse indole derivatives forming new Csp 3 ‐Csp 2 bond. The silver carbonate used as a glycosyl activator, enabling the stereoselective formation of a wide array of 3‐indolyl‐ C ‐glycosides and N ‐orthoesters type products, depending on electron‐donating group and electron‐withdrawing group substitution on Indole substrates, with good isolated yields at room temperature. Quantum mechanical calculations revealed interesting findings towards product distribution. A key feature of this method is mild reaction conditions, easy workup along with the use of a nontoxic and biocompatible activator.