Interaction, bond formation or reaction between a dimethylamino group and an adjacent alkene or aldehyde group in aromatic systems controlled by remote molecular constraints

Abstract

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.