Bicyclopropylidene smoothly undergoes 1,3-dipolar cycloadditions to nitrones or nitrile oxides under different reaction conditions. The strained bisspirocyclopropanated isoxazolidines obtained from nitrones easily rearrange upon heating with selective opening of one of the two spirofused cyclopropane rings. This process produces 4-pyridone, 7-indolizinone, and 2-quinolizinone derivatives containing a spirocyclopropane moiety in the alpha-position to the carbonyl group in good yields. The same sequence of cycloaddition and rearrangement can be achieved in a "one-pot" operation with considerable benefit for the reaction yield. Bisspirocyclopropaneisoxazolines obtained from nitrile oxides are more stable than their saturated counterparts and rearrange only at higher temperature less chemoselectively. Opening of both spiro-fused cyclopropyl rings followed by aromatization produces interesting 2-substituted dihydrofuro[2,3-c]pyridine derivatives.

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A series of 3-spirocyclopropane-tetrahydropyrid-4-ones has been synthesized by the method consisting of nitrone cycloaddition to bicyclopropylidene and thermal rearrangement of the adducts. Regioisomeric 5-spirocyclopropanetetrahydropyrid-4-ones and 5-spirocyclopropanedihydropyrid-4ones were instead obtained by cycloaddition of nitrones and nitrile oxides, respectively, to methylenespiropentane, followed by thermal rearrangement. Methylenedispiro[2.0.2.1]heptane gave, in turn, 5,6-bis(spirocyclopropane)dihydropyrid-4-ones. The new compounds were prepared as simple aza analogues of the cytotoxic natural products illudins and ptaquiloside in order to study their activity in cleaving a DNA plasmid. The activities shown by several of the compounds are moderate, but from a comparative qualitative analysis of the results a useful structure-activity relationship for this new class of compounds could be derived.

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