Pyranones play an important role towards the synthesis of carbohydrate containing natural products and are the key building blocks for most of the natural/unnatural oligosaccharides. Boc-Pyranones synthesis is a De Novo approach (i.e, achiral starting material, 2-acetyl furan (1) converted to chiral products) via Noyori asymmetric hydrogenation, Achmatowicz oxidative rearrangement, Upjohn dihydroxylation. Particularly, Boc-protected pyranones have established broad applications towards the synthesis of natural/unnatural products containing carbohydrate motifs (e.g., total synthesis of mezzettiasides, a class of partially acetylated anti-cancer natural products via Pd-/B-dual catalysis and synthesis of cleistriosides/cleistetrosides, a series of rhamno-oligosaccharides).