Interaction of Aryloxychlorocarbenes with Acetylenedicarboxylate: Novel Formation of Polyfunctional Butadienes and 8-Oxatricyclo[3.2.1.0^2.4]oct-6-enes

The interaction of aryloxychlorocarbenes with dialkyl acetylenedicarboxylates has been examined. Thermolyses of 3-aryloxy-3-chlorodiazirines in the presence of acetylenedicarboxylate resulted in the formation of unexpected polyfunctional 1,3-butadienes and 8-oxatricyclo[3.2.1.02.4]oct-6-enes or of 2-aryoxycarbonylmaleates dependent upon reaction conditions. This work confirmed the nucleophilicity of aryloxychlorocarbenes and underlined their synthetic potential.