Carbohydrates play important roles in medicinal chemistry and biochemistry. However, their synthesis relies on specially designed glycosyl donors, which are often unstable and require multi-step synthesis. Furthermore, the catalytic and stereoselective installation of arylated quaternary stereocentres on sugar rings remains a formidable challenge. Here we report a facile and versatile method for the synthesis of diverse C–R (where R is an aryl, heteroaryl, alkenyl, alkynyl or alkyl) glycosides from readily available and bench-stable 1-deoxyglycosides. The reaction proceeds under mild conditions and exhibits high stereoselectivity across a broad range of glycosyl units. This protocol can be used to synthesize challenging 2-deoxyglycosides, unprotected glycosides, non-classical glycosides and deuterated glycosides. We further developed the catalyst-controlled site-divergent functionalization of carbohydrates for the synthesis of various unexplored carbohydrates containing arylated quaternary stereocentres that are inaccessible by existing methods. The synthetic utility of this strategy is further demonstrated in the synthesis of pharmaceutically relevant molecules and carbohydrates.

碳水化合物在药物化学和生物化学中发挥着重要作用。然而，它们的合成依赖于专门设计的糖基供体，这些供体通常不稳定并且需要多步合成。此外，在糖环上催化和立体选择性安装芳基化四元立体中心仍然是一个艰巨的挑战。在这里，我们报告了一种简便且通用的方法，用于从易于获得且实验室稳定的 1-脱氧糖苷合成各种 C–R（其中 R 是芳基、杂芳基、烯基、炔基或烷基）糖苷。该反应在温和的条件下进行，并且在广泛的糖基单元上表现出高立体选择性。该方案可用于合成具有挑战性的2-脱氧糖苷、未保护的糖苷、非经典糖苷和氘代糖苷。我们进一步开发了催化剂控制的碳水化合物位点发散官能化，用于合成各种未开发的碳水化合物，这些碳水化合物含有现有方法无法获得的芳基化四元立构中心。该策略的合成效用在药学相关分子和碳水化合物的合成中得到进一步证明。