Synthesis and unusual [2+2]-cycloaddition reactions of ethyl 4-chloro-2-oxobut-3-ynoate with unactivated alkenes

The highly activated acetylenes, ethyl 4-chloro-2-oxobut-3-ynoate and ethyl 4-bromo-2-oxobut-3-ynoate, were prepared from readily available bis(trimethylstannyl)acetylene in two steps with high overall yield. An unusual ability of the former to furnish [2+2]-cycloadducts with 1,1-disubstituted alkenes in the absence of irradiation and catalysts was discovered. The cycloaddition of ethyl 4-chloro-2-oxobut-3-ynoate to the 1,2-disubstituted alkenes was shown to be effectively catalyzed with stannic chloride.