Chlorotrimethylsilane-Zinc chloride

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. 

Reductive coupling of carbonyls to alkenes Titanium(IV) chloride-Zinc, 310 of carbonyls to pinacols Titanium(III) chloride, 302 Titanium(IV) chloride-Zinc, 310 of other substrates Samarium(II) iodide, 270 Reductive cyclization 2-(Phenylseleno)acrylonitrile, 244 Tributylgermane, 313 Tributyltin hydride, 316 Triphenyltin hydride, 335 Trityl perchlorate, 339 Reductive hydrolysis (see Hydrolysis) Reductive silylation Chlorotrimethylsilane-Zinc, 82... 

Metal-containing compounds, Zinc Compounds (Continued) (Carboethoxyalkyl)zinc iodide, 220 (Carboethoxyethyl)zinc iodide, 220 (Carboethoxypropyl)zinc iodide, 220 Chlorotrimethylsilane-Zinc, 82 (Cyanomethyl)zinc bromide, 221 Dibromomethane-Zinc-Copper(I) chloride, 93... 

SULFOXIDES Chlorotrimethylsilane- Zinc. Sodium borohydride-Cobalt(II) chloride. DESILYLATION Cesium fluoride. Potassium /-butoxide-Dimethyl sulfoxide. Potassium hydride. 

The newest techniques employ silylation. Even the anions of saturated butenolides afford the enol ester on reaction with chlorotrimethylsilane91 applied to a butenolide the method readily supplies a 2-silyloxyfuran. Such ethers are even more easily procured by allowing a butenolide to react with chlorotrimethylsilane in the presence of triethylamine and zinc chloride but for reasons that remain unclear, acetonitrile is the only satisfactory solvent.92 A typical transformation of 2-trimethylsilyloxyfuran is shown in Scheme 19. 

Chelation-controlled diastereoselective addition to a-silyloxy aldehydes has been achieved using dialkylzincs and chlorotrimethylsilane the chelation is promoted by in situ ethyl zinc chloride. This autocatalysis means that stoichiometric amounts are not needed. 

In indium-mediated reactions, a catalytic use of expensive indium is desirable from an economical standpoint, and it has been achieved in combination with more electron-positive metals. Thus, allylation of aldehydes and ketones, as well as prenylation of 2-chlorobenzoquinone, has been performed by using metallic aluminum or zinc in combination with a catalytic amount of indium(m) chloride.63 Also, allylation of aldehydes and ketones with allyl bromide is carried out with a catalytic amount of indium powder (from 0.01 to 0.1 equiv.) in THF in the presence of manganese and chlorotrimethylsilane as the reducing and oxophilic agents, respectively (Scheme 2). 64,65... 

The bis(silyloxy)cyclohexadienes (35) and (36) are prepared by treatment of the readily available keto trialkylsilyl enol ethers with lithium di-isopropylamide and chlorotrimethylsilane. The isomeric compound (37) is prepared by treatment of cyclohexane-1,4-dione with triethylamine, zinc(ii) chloride, and chlorotrimethylsilane. 

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