The scope of suitable nucleophilic partners in 2-deoxy-βglucosylation reactions with electrophile 2a promoted with catalyst 1a was explored (Figure ). Focus was placed on couplings where mild conditions would be advantageous compared to existing protocols that rely on either stoichiometric metal amide base or catalytic strong Lewis acids. Reactions were performed with two equivalents of 2a to compensate for unproductive consumption of electrophile through elimination and hydrolysis pathways. Alcohols bearing base-sensitive functional groups, such as protected amino acids (3a-3b) or pleuromutilin (3e), which possesses an enolizable stereocenter, underwent reaction with high βselectivity without erosion of stereopurity. Deoxy-sugarbased acceptors (3c and 3d) were excellent substrates, yielding disaccharides with high selectivity and efficiency. Alcohols with acid-sensitive functionalities, including hemiacetals (3f and 3j), tertiary amines (3g and 3i), and aromatic heterocycles (3h), also underwent 2-deoxyglucosylation by the catalytic approach. Basic alumina was required for substrates with basic-nitrogen functionality (3g-3h, 3m) to prevent the formation of ammonium phosphate salts, which inhibit thiourea catalysts. The particularly challenging alcohols 3h-3j possessing both base-and acid-sensitive functionality were also found to be suitable substrates under the catalytic conditions.