Cobalt-Catalyzed Intermolecular [2+2] Cycloaddition between Alkynes and Allenes

An intermolecular [2+2] cycloaddition reaction between an alkyne and an allene is reported. In the presence of a cobalt(I)/diphosphine catalyst, a near equimolar mixture of the alkyne and allene is converted into a 3-alkylidenecyclobutene derivative in good yield with high regioselectivity. The reaction tolerates a variety of internal alkynes and mono- or disubstituted allenes bearing various functional groups. The reaction is proposed to involve regioselective oxidative cyclization of the alkyne and allene to form a 4-alkylidenecobaltacyclopentene intermediate, with subsequent C−C reductive elimination.