Synthesis of 1,1-bis(silyl)-1-alkene derivatives bearing Si-H functional groups via Peterson protocol

Various aromatic aldehydes were converted to one-carbon elongate 1,1-bis(silyl)-1-alkene derivatives bearing Si-H functional and reactive groups in a convenient one-pot operation via the Peterson protocol. Then poly(styrene) and poly(α-methylstyrene) (?&II) random homopolymers were synthesized by solution free radical polymerization at 70(±1) °C using α,α′-azobis(isobutyronitrile) (AIBN) as an initiator. The aldehyde group is introduced by direct electrophilic substitution of polymers ? and II. This formylation reaction was conducted in two different solvents: dichloromethane (CH₂Cl₂) and nitrobenzene (PhNO₂). The results indicate that PhNO₂ appeared to be a more suitable solvent for such an aldehyde functionalization of the polymers. The formylated polymers (I_CHO, II_CHO) were then converted to Si-H functionalized polymers (I_Si-H, II_Si-H) via reaction with tris(dimethylsilyl)methyllithium, (HMe₂Si)₃CLi.