Switchable Reactivity of Glycals Toward the Synthesis of 3‐Oxo Glycals and 2‐Deoxy Lactones

The switchable reactivity of glycals has been demonstrated by the successful synthesis of 3‐oxo glycals and 2‐deoxy lactones directly from glycals under ambient conditions. 3‐Oxo glycals were obtained from various glycals via C3‐oxidation employing (NH 4 ) 2 S 2 O 8 as an oxidant in DMSO solvent at 55 °C. However, 2‐deoxy lactones were synthesized through C‐1 oxidation using Pd(OAc) 2 as a catalyst and K 2 S 2 O 8 as an oxidant in the DMSO:H 2 O solvent system. The methodology is operationally simple, high‐yielding, scalable, and endowed with varied substrate scope.