Imparting stereochemistry in the quaternary centres of structurally intriguing and biologically potent natural products and building blocks is a daunting challenge in asymmetric synthesis. Thus, constructing stereo-defined quaternary centres in densely functionalised nature's chiral pools, for instance, carbohydrates, may need a unique approach due to their several multi-functionalised stereoisomers and structural rigidity. In general, the presence of quaternary centres in the carbohydrate moiety as a part of the bioactive molecule accounts for its crucial inherent bioactivity, resulting in them becoming a synthetic challenge to researchers. This review focuses primarily on the installation of quaternary stereocentres in the carbohydrate unit of biologically and pharmaceutically active molecules and building blocks.