Novel transannular reactions in the acid hydrolysis of diazotized syn- and anti-4-amino[2.2](1,4)naphthalenoparacyclophanes

Abstract

The diazonium ions derive from the title syn- and anti-4-aminocyclophnes 1a and 4a in aqueous solution undergo transannular reactions to give 17-hydroxy[2.2](1,4)naphthaenoparacyclophane 3a and 9,10-dihydro-1,9:4,10-diethano-9,10-ethenoanthracene 6a, respectively. Deuterium-tracer experiments suggest that the reaction of diazotized 1a proceeds via a pathway involving transannular diazo coupling followed by generation of a 16,17-didehydro intermediate. On the other hand, the reaction patway of diazotized 4a involves dediazoniation followed by transannular electrophilic addition.