Interaction, Bond Formation or Reaction Between a Dimethylamino Group and an Adjacent Alkene or Aldehyde Group in Aromatic Systems Controlled by Remote Molecular Constraints.

Peri–peri interactions in naphthalene systems control the degree of bond formation between a peri-dimethylamino group and a polarised alkene or aldehyde group. Two peri-phenyl groups, which repel, induce closer N⋯C interactions or bond formation, while the ethylene link in the corresponding acenaphthene system has the opposite effect, and for the more electron-deficient alkenes lead to formation of a fused azepine ring initiated by the tert-amino effect. In related 1,8-fluorene derivatives N⋯C interactions occur for an aldehyde and a moderately polarised alkene, but fused azocines are formed when the alkene is more reactive.