A one‐pot, two‐step synthesis of chiral 7‐oxa‐1‐azabicyclo[2.2.1]heptane derivatives from unprotected D‐xylose was achieved by an intramolecular 1,3‐dipolar cycloaddition of the N‐(γ‐alkenyl)‐substituted nitrone intermediate. The stereochemical course of the cycloaddition was altered by the addition of an achiral Lewis acid. The bicyclic byproducts were employed in a concise synthesis of two new enantiomeric piperidine‐type iminosugars.