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) (І&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 І 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 (ICHO, IICHO) were then converted to Si–H functionalized polymers (ISi–H, IISi–H) via reaction with tris(dimethylsilyl)methyllithium, (HMe2Si)3CLi.

A variety of non-enolizable benzaldehyde derivatives and polymers containing formyl groups are converted to the corresponding 1,1-bis(silyl)-1-alkenes in one-pot procedure involving the addition of (HMe2Si)3CLi to carbonyl groups.Figure optionsDownload as PowerPoint slide