The cobalt-catalyzed [6+2] cycloaddition of cyclooctatetraene 1 with alkynes 3 affords monosubstituted bicyclo[4.2.2]deca-2,4,7,9-tetraenes 4 in fair to good yields. Due to the valence tautomerism, 1,3,5-cyclooctatriene 2, in equilibrium with bicyclo[4.2.0]octa-2,4-diene A, and alkynes 3 are converted to 10 and 11 according to [6+2] and [4+2] cycloadditions, respectively.
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