On the Conrotatory Ring Opening of 3-Carbomethoxycyclobutene Vis-À-Vis 3-Carbomethoxy-1,2-Benzocyclobutene and the Predominant Inward Opening of 3-Dimethylaminocarbonyl-1,2-Benzocyclobutene

The torquoselectivity of conrotatory ring opening of 3-carbomethoxycyclobutene is controlled by p C1C2 →s* C3C4 and s C3C4 →p* CO interactions in the transition state in a 4-electron process as opposed to only s C3C4 →p* CO interaction in an apparently 8-electron event in 3-carbomethoxy-1,2-benzocyclobutene. The ring opening of 3-carbomethoxy-1,2-benzocyclobutene is sufficiently endothermic. We therefore argue that the reverse ring closing reaction is faster than the forward ring opening reaction and, thus, it establishes an equilibrium between the two and subsequently allows formation of the more stable species via outward ring opening reaction. Application of this argument to 3-dimethylaminocarbonyl-1,2-benzocyclobutene explains the predominantly observed inward opening.