Solvolysis of N-Chloro-1,4-dihydro-1,4-iminonaphthalenes (7-Azabenzonorbornadienes); Dependence of the Rearrangement Pathway on the Configuration at Nitrogen

Article abstract of DOI:10.1016/0040-4020(95)00336-7

N-Chloro- derivatives of the 1,4-dihydro-1,4-iminonaphthalene (7-azabenzonorbornadiene) ring system undergo silver (I)-assisted rearrangement with participation of etheno- (syn-chloro- series) or benzo- (anti-chloro- series) ?-electrons.The high barriers to inversion at nitrogen together with some control over the ratio of invertomers allow observation of a different reaction pathway for each invertomer when reactions are performed at low temperatures; approaches which allow selection of the benzo- participation route (giving 6,7-benzo-derivatives of the 1-azabicyclo<3.2.0>hept-3-ene ring system) are described.