Orbital topology. III. Orbital mapping of unsymmetrical molecules. A survey of the thermal ring opening of isoelectronically substituted cyclobutenes and benzocyclobutenes

Abstract

AbstractOrbital mapping analysis based on CNDO/2 molecular orbitals has been used to survey the thermal ring‐opening isomerizations of cyclobutenes and benzocyclobutenes. Isoelectronic substitutions within the molecular framework of cyclobutene (e.g., CH2 replaced by CH−, OH+, NH, NH2+) result in ground‐state orbital correlations via both conrotatory and disrotatory pathways in several cases, in contrast to the parent hydrocarbon conrotatory stereochemistry. The results substantiate the heteroatom effects previously revealed by orbital mapping for the disrotatory thermal isomerizations of isoelectronic Dewar benzenes. Qualitative patterns, such as nodal shifts in the butadiene π orbital, are discussed in relation to the mapping correlations. The isoelectronic benzocyclobutenes give ground‐state orbital correlations via conrotatory pathways only, which suggests that delocalization may reduce the heteroatom perturbation.