Silylmethyl chlorides

Deprotonation of 2- and 4-pyridones is easily achieved, and the anions react with carbon electrophiles, such as carbon dioxide and trimethyl-silylmethyl chloride, at nitrogen, but with trimethylsilyl chloride at oxygen (Scheme 2.25). 

Thousands of papers and patents have appeared on the direct synthesis of organochlorosilanes since 1940 when Rochow reported the direct reaction.4 These results are comprehensively accounted for in a number of earlier reviews and books.3 8 The purpose of this review is to describe the recent developing trend of the direct reaction of elemental silicon with activated or unactivated alkyl chlorides, in particular, emphasizing direct reactions with a mixture of hydrogen chloride and activated alkyl chlorides such as polychlorinated methanes, silylmethyl chlorides and dichlorides, allyl chloride, etc. 

Arsonium Trimethyl-(trimethyl-silylmethyl)- (chlorid) X1II/8, 402... 

Treatment of j]2-iminosilaacyl complex 6c with LiEt3BH gave azazircona-cyclopropane 10, which was hydrolyzed to give (silylmethyl)aniline in 82% yield (Scheme 5). Treatment of 10 with 4-octyne gave alkene 12 in 73% yield after hydrolysis. Presumably, the insertion of alkyne into the carbon-zirconium bond of 10 gives silazirconacyclopentene 11. When CuCl and allyl chloride were added to a THF solution of silazirconacyclopentene 11, tetrasubstituted alkene... 

Aerobic oxidation of trimethylsilylmethylmagnesium chloride in the presence of a-methylstyrene results in addition of trimethyl-silylmethyl radical to the carbon-carbon double bond followed... 

The first 1-metalloadamantane (38) has been prepared in 50% yield by the acid catalysed redistribution of silylmethyl substituted cyclohexanes [equation (42)]. A s ies of substituted adamantyl derivatives have been prepared from the chloride by cleava of the appropriate trimethylsilyl derivative [equation (43)]. 1-Adamantyltrichlorosilane has been made by the gas phase interaction of AdCl with SiCla and SiaCle, and derivatives have been prepared, as have a variety for 1,3,5,7-tetrasila-adamantane. ... 

The N-silylmethylamides are formed by reaction of an acyl halide (commonly used acyl chloride) with the desired N-silylmethylamine (Scheme 24.10). This method is very extensively applied not only for the synthesis of N-silylmethylated amides, but also for the relevant imides and carbamates (Table 24.4) (37,55,68-74). 

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