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.本研究考察了芳氧基氯卡宾与乙酰二羧酸二烷基酯之间的相互作用。在乙酰二羧酸二烷基酯存在的条件下对3-芳氧基-3-氯双吖丙啶进行热解，可根据反应条件的差异，意外生成多官能团1,3-丁二烯、8-氧杂三环[3.2.1.02.4]辛-6-烯，或是2-芳氧基羰基马来酸酯。本研究证实了芳氧基氯卡宾的亲核性，并凸显了其合成应用潜力。