Synthesis of Substituted 1,5‐Dioxaspiro[2.4]heptanes from 2,3‐ Dichloroprop‐1‐ene

The 4,4′‐di(tert‐butyl)biphenyl(DTBB)‐catalyzed lithiation of 2,3‐dichloroprop‐1‐ene ( 10 ) in THF at 0°, in the presence of symmetrically substituted ketones, led to the corresponding methylene‐substituted diols 11 (Scheme 2), which, by treatment with NaH and I₂ in THF at room temperature, furnished a series of 1,5‐dioxaspiro2.4]heptanes 14 (Scheme 4). Oxidation of compounds 14 with RuO₄ gave the corresponding lactones 16 . Compounds 14 and 16 are structural units present in many biologically active natural compounds and in versatile intermediates in synthetic organic chemistry.