Upon treatment of fructose‐derived nitrone 1 with samarium diiodide, with the aim of inducing its umpolung and coupling with electrophiles, an unexpected β‐elimination of the benzyloxy group at C‐1 was observed, yielding nitrone 2. The mechanism and scope of this transformation were investigated, from nitrone 1 and from five other α‐alkoxy or α‐acyloxy nitrones. This paper describes the preparation of new nitrones 3 and 4 from d‐fructose; their synthesis demonstrates that acyl‐protected nitrones can be prepared efficiently by intramolecular N‐alkylation of sugar‐derived oximes, a strategy previously developed only for ether‐ or ketal‐protected cyclic nitrones. Nitrones 3 and 4 underwent fast β‐elimination upon treatment with SmI2. Contrastingly, no β‐elimination occurred with nitrones 5–7, suggesting a specific behavior of endocyclic keto nitrones.