Methyllithium-Chlorotrimethylsilane

A route involving trapping the enolate as a silyl enol ether, subsequent transme-tallation to the corresponding lithium enolate and alkylation turned out to be more efficient (Scheme 18.41) [123]. Thus, treatment of 120 with the cuprate 124 and chlorotrimethylsilane furnished the silyl enol ether 125, which was then converted into the desired enprostil derivative 127 with 68% yield over both steps by reaction with methyllithium and the allenic triflate 126. 

The a-arylamino nitriles 251, obtained from primary aromatic amines, trimethylsilyl cyanide and acetone in the presence of zinc chloride, react with methyllithium to give A-t-butylarylamines 252287. Af,Af-Bis(trimethylsilyl)amines 253 (R = allyl, benzyl, 3-phenylpropyl etc.) are formed in 50-88% yields by the action of chlorotrimethylsilane on primary amines in the presence of a catalytic amount of titanium(IV) chloride288. 

Methyllithium (4.0 mmol, 1.0 M in diethyl ether, 4.0 mL) was added to a suspension of CuCN (2.0 mmol, 0.18 g) in THF (10 mL) at -75°C. The reaction mixture was then stirred until a clear solution was obtained and allowed to warm to room temperature. The appropriate (Z)-vinylic telluride A (2.0 mmol) or B (1.0 mmol) was added and stirred for 45 min. The solution was cooled back to -75°C and the corresponding enone (2.2 mmol) was added. After 20 min, chlorotrimethylsilane (2.6 mmol, 0.60 g) diluted in THF (5 mL) was added. The reaction mixture was stirred for 1 h, allowed to warm to room temperature and then treated with 1 1 solution of saturated aqueous NH4CI and NH4OH (20 mL), extracted with ethyl acetate (3x20 mL), dried, evaporated and the residue was purified by Kiigelrohr distillation affording the silyl enol ethers. 

Treatment of chromium hexacarbonyl with methyllithium, followed by addition of chlorotrimethylsilane, gave a silylated carbene complex (114), which decomposed above 40° ... 

Allylic phosphorus compounds Tris(tetrabutylammonium) pyrophosphate, 338 Allylsilanes t-Butyllithium, 58 Chlorotrimethylsilane-Lithium, 81 Lithium bis(dimethylphenylsilyl)-cuprate, 161 Methyllithium, 188 Trichlorosilane-t-Amines, 322 Allylic sulfur compounds (Phenylsulfonyl)allene, 247 Sodium benzenesulfinate, 289... 

The silyl organoaluminum reagent (52) was prepared either by the addition of activated aluminum to a tetrahydrofuran solution of chlorotrimethylsilane, or by the treatment of sodium tetrakis(trimethyl-silyl)aluminate with aluminum chloride. Alternatively, ate complex (53) may be prepared by the addition of methyllithium to tris(trimethylsilyl)aluminum. ... 

Chlorotrimethylsilane Silane, chlorotrimethyl- (8,9) (75-77>4) Tetrachlorosilane Silicon chloride (8) Silane, tetrachloro- (9) (10026-04-7) Methyllithium-lithium bromide complex Lithium, methyl- (8,9) (917-54-4)... 

The reaction of the readily accessible trimethylsilyl enol ethers with methyllithium has been successfully applied to prepare ethereal solutions of lithium alkenolates RCH=CHOLi [3,5]. Good results can be obtained also with n-BuLi [4]. Both the trimethylsilyl enol ethers, which are prepared hy heating a mixture of the aldehyde, chlorotrimethylsilane, triethylamine and DMF, and the enolates are mixtures of the E- and Z-isomers. 

These experiments also enabled the discovery of catalytic enantioselective protonation. [46] Highly ( )- enriched, pure hthium enolate (98 2) was obtained hy a Grignard reaction, addition of chlorotrimethylsilane, fractional distillation and treatment with methyllithium. For the stereoselective protonation, 0.2-0.3 equivalents of isopropylephedrine were sufficient, because this was re-... 

Preparative Method from methoxy(phenylthio)methyllithium with chlorotrimethylsilane. ... 

Excess methyllithium reacted with dodecamethylcyclohexasilane in a mixture of tetrahydrofuran and ether evidently in a manner similar to that observed with the phenylated cyclic compounds. Subsequent to treatment of the reaction mixture with chlorotrimethylsilane, there was obtained a complex mixture of products. Judging from their boiling points, the products were composed of permethylated polysilanes containing three to seven or eight silicon atoms.Only decamethyltetrasilane and dodeca-methylpentasilane were isolated in a relatively pure state. 

---