12. Syntheses and Reactions of Alkylthio- And Arylthio-Substituted 1,6-Methano[10]annulenes

Article abstract of DOI:10.1002/hlca.19970800113

The treatment of bromo-substituted 1,6-methano[10]annulenes with sodium thiolates in DMF provides easy access to alkylthio- and arylthio-substituted 1,6-methano[10]annulenes (Schemes 2-4). These compounds are then brominated with N-bromosuccinimide (NBS) to study their reactivity in electrophilic substitution reactions (Schemes 5 and 6). The resulting brominated thio-1,6-methano[10]annulenes are, in a subsequent reaction, subjected to Heck coupling with (4-nitrophenyl)acetylene (13) to produce the alkynylated derivatives 14 in reasonable yield (Scheme 7).