Silylation Bromomethyl chlorodimethylsilane

Silylation (see also Protection of alcohols) (Bromomethyl)chlorodimethylsilane, 316 /-Butyldimethylchlorosilane, 92 Chloromethyldiphenylsilane, 74 Chloromethyltrimethylsilane, 76 Di-/-butylmethylsilyl trifluoromethanesul-fonate, 95... 

Use as an Electrophile. The chlorosilane function is highly electrophilic and can react with a variety of nucleophiles, for instance with an aryllithium carbanion, to provide silyl derivatives. The (bromomethyl)chlorodimethylsilane can also be utilized as a bis-electrophilic reagent, thanks to the bromomethylene function. Initial substitution of chlorine by an aryllithium or an aryl Grignard followed by the displacement of bromine by a phenoxide anion provided valuable linkages for solid phase s)m-thesis. Based on the same idea, Martin proposed a new synthesis of unsymmetrical C-aryl glycosides. Orthometallation of a furyl moiety followed by silylation sets a diene on a silicon tether. The masked dienophile (a benzyne) is then introduced by 0-alkylation. The cycloadduct was then converted to various naphthol derivatives (eq 25). 

Alkylation of (bromomethyl)chlorodimethylsilane by the acetylide anion followed by addition of the thioacetate anion opened a new access to a silyl tethered yne-vinylsulflde precursor that found use in new radical cascades. Unsymmetrical ansa-fluorenyl containing ligands incorporating a CFl2-SiMe2 bridge have been described and result from a dialkylation with fluorenyl carbanions. ... 

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