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.

Graphical abstractA 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 full-size imageDownload as PowerPoint slide