Bis trimethylsilylmethyl

Heating of bis(trimethylsilylmethyl)sulfoxide 1166 generates HMDSO 7 and, via 1167, the reactive intermediate thioformaldehyde-S-methyhde 1168, which can be trapped in situ, e.g. by N-methylmaleimide, to give 81% of the l,3-dipolar cycloaddition product 1169 [14] (Scheme 8.3). Further analogous 1,3-dipolar cycloadditions with acetylenes are discussed elsewhere [15]. 

It bums spontaneously in air and reacts violently with water, as does the congener, bis(trimethylsilylmethyl)aluminimn bromide. 

Bis(trimethylsilylmethyl)zinc 1 is synthesized by the addition of 2 equiv. of trimethylsilylmethylmagnesium bromide to anhydrous zinc bromide, as shown in Scheme 1. 

After removal of MgBr2 by filtration, bis(trimethylsilylmethyl)zinc 1 can be distilled at 41 °C and 0.1 torr.24... 

Bis(trifluoromethyl)cadmium-l,2-dimethoxyethane adduct, 0587 =1= Bis(trimethylsilylmethyl)magnesium, 3099... 

Bis(trimethylsilyl)hydrazine, 2612 Bis(trimethylsilyl)mercury, 2589 Bis(trimethylsilylmethyl)magnesium, 3093... 

Primary amines.9,22,62 Direct amination of chloromethyl-trimethylsilane illustrates the diliiculty of stopping the reaction at the monoalkylation level with the formation of up to 30% of the bis(trimethylsilylmethyl) amine even when a large excess of ammonia is employed. The same process has been used to prepare aminomethylsiloxanes where the formation of a small amount of the secondary amine is also observed.63 See also Ref. 24. 

Azomethine ylids can be generated photochemically by irradiating N-protected bis(trimethylsilylmethyl)amines in the presence of a sensitizer (1,4-dicyano-naphthalene, DCN ) in methanol as the solvent. The ylid reacted with a series of dipolarophiles to give adducts in moderate to good yields.446,447... 

Conveniently N-protected 2,2/-bis(trimethylsilylmethyl)pyrrolidine, -piperidine and -azepane were prepared and reacted with phenylvinylsulfone in the presence of silver fluoride (2 equiv.). The X-azabicyclo[m.2.1]alkane framework in each case is obtained in good to excellent yields. Being very efficient, this technique provides a new strategy to synthesize tropinone, an important member of the tropane class of alkaloids.451... 

The use of another type of bis(trimethylsilylmethyl)amine leads to the synthesis of l-azabicyclo[m.3.0]alkanes also present in the skeleton of a number of alkaloids as trachelanthamidine, isoretronecanol, and tashiramine.447 451... 

Trunethylsilylmethylpotassium, KCH2Si(CH3)3. This base is prepared by reduction of bis(trimethylsilylmethyl)mercury with potassium sand. It is comparable in reactivity to n-BuLi/KOC(CH,)3 for allylic and benzylic metallation. ... 

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