Abstract Metalation of vinyltrimethylsilane and both trans-(VIII) and cis-(IX) 1-(trimethylsilyl)- 3, 3-dimethyl-1-butene with organolithium/TMEDA complexes was explored. Vinyltrimethylsilane underwent exclusive addition of tert-butyllithium to the double bond. Metalation of (VIII) occurred only at the trimethylsilyl function, while (IX) afforded both α- silylvinyl and trimethylsilyl position metalation.
