Synthesis of New Functional Acenaphthylene Derivatives. 2. Regioselective Electrophilic Substitution of Silylated Acenaphthenes and Acenaphthylenes

Article abstract of DOI:10.1021/jo00347a008

New silylated derivatives have been synthesized in the acenaphthylene series <5-(trimethylsilyl)acenaphthene (1a) and -acenaphthylene (3a), 4,5-bis(trimethylsilyl)-4,5-dihydroacenaphthene (6), and 4,5,7,8-tetrakis(trimethylsilyl)-4,5,7,8-tetrahydroacenaphthene (7)> by appropriate silylation reactions, followed by oxidation in the case of 3a. 1a and 3a as well as 1-(trimethylsilyl)-and 1,2-and 1,5-bis(trimethylsilyl)acenaphthylenes (2a, 4a, and 5a, respectively) have been used as regioselective precursors of 5-functional acenaphthenes and 1-monofunctional and 1,2-and 1,5-bifunctional acenaphthylenes by electrophilic substitution of the trimethylsilyl group(s).Mono- and bisulfonations succeeded in all cases as well as the acylation or iodination of monosilyl derivatives and 1,2-diodination of 4a.Thus, various novel functional acenaphthenes and acenaphthylenes could be prepared by a convenient route.In contrast, attempts at diodination of 5a and diacylation of 4a and 5a were unsuccessful.