Alkylidenecyclopropanone acetals reaction with furans

Ring opening reaction of alkylidenecyclopropanone acetals readily proceeds in the presence of Lewis or Bransted acids to produce l-alkylidene-2-oxyallyl cation, which is provided for the reaction with nucleophiles such as chloride, alcohols, siloxyalkenes, and furans. The reaction of this cation with the carbon nucleophiles gives products of [4 + 3] and [3 + 2] cycloaddition as well as those of nucleophilic addition. The modes of addition reactions are controlled by the oxy group of the cation and by the reaction conditions including solvent. 

We have recently developed a novel method for the generation of alkylideneallyl cations from alkylidenecyclopropanone acetals (8, 9). This method provides a nice opportunity to examine the selectivity of reactions of the ambident cation with various nucleophiles including siloxyalkenes (10) and furans (11). The reaction of the cation with the carbon nucleophiles gives [4 + 3] and [3 + 2] cycloaddition products as well as simple nucleophilic addition products. These results are summarized in this chapter. 

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