Silylation electroreductive

In a similar type of process, imines have been dimerized to give 1,2-diamines, by a number of procedures, including treatment with TiCLj—In/aqueous EtOH, Zn/aqueous NaOH, Cp2VCl2/Zn/PhMe2SiCl, with Sml2, and I for silylated imines) NbCl4(thf)2. When electroreduction was used, it was even... 

In this section primarily reductions of aldehydes, ketones, and esters with sodium, lithium, and potassium in the presence of TCS 14 are discussed closely related reductions with metals such as Zn, Mg, Mn, Sm, Ti, etc., in the presence of TCS 14 are described in Section 13.2. Treatment of ethyl isobutyrate with sodium in the presence of TCS 14 in toluene affords the O-silylated Riihlmann-acyloin-condensation product 1915, which can be readily desilylated to the free acyloin 1916 [119]. Further reactions of methyl or ethyl 1,2- or 1,4-dicarboxylates are discussed elsewhere [120-122]. The same reaction with trimethylsilyl isobutyrate affords the C,0-silylated alcohol 1917, in 72% yield, which is desilylated to 1918 [123] (Scheme 12.34). Likewise, reduction of the diesters 1919 affords the cyclized O-silylated acyloin products 1920 in high yields, which give on saponification the acyloins 1921 [119]. Whereas electroreduction on a Mg-electrode in the presence of MesSiCl 14 converts esters such as ethyl cyclohexane-carboxylate via 1922 and subsequent saponification into acyloins such as 1923 [124], electroreduction of esters such as ethyl cyclohexylcarboxylate using a Mg-electrode without Me3SiCl 14 yields 1,2-ketones such as 1924 [125] (Scheme 12.34). 

Utilization of the electroreduction of aryltrimethylsilanes and aryltrimethylgermanes for the preparation of silyl- and germyl-substituted cyclohexadienes was extensively studied203, for example ... 

Selective silylation of polychloromethanes using reactive metal electrodes such as zinc and magnesium has also been reported as shown in Scheme 37 [76, 77]. The electroreduction of carbon tetrachloride and chloroform in the presence of chlorotrimethylsilane affords the monosilylated and disilylated products. The product selectivity seems to depend upon the electrode material. 

Electroreductive coupling of ketones with silyl-substituted olefins promotes interesting reactions that are useful for organic synthesis. For example, coupKng of ketones with trimethylvinylsilanes affords /I-trimethylsilyl alcohols, which are easily transformed to the corresponding olefins (Scheme 40). This reaction is interesting from the synthetic point of view since vinylsilane behaves as the equivalent to a /I-trimethylsilyl group-substituted anion [77, 83]. 

Very few transition-metal catalyzed electroreductive carbon-heteroatom bond formations have been described. The electrochemical silylation of allylic acetates was carried out in the presence of Pd-PPha [131]. The electrosynthesis of arylthioethers from thiophenol and aryl halides [132] and the coupling of bromobenzene with dichlorophenylphosphine [133] were performed with Ni-bpy as catalyst. 

Similar electroreductive silylation of a series of unsaturated nitrogen compounds such as trimethylsilyl cyanide, cyanamide or isocyanide, bis(trimethylsilyl)carbodiimide and trimethylsilyl isocyanate provide precursors of bis(trimethylsilyl)methylamine, which is useful for organic synthesis (equations 90 and 91)115. This electrochemical method is a safer and more economical process compared with the chemical process using an alkali metal such as lithium. 

A parallel study of the silylation of thiobenzamides in acetonitrile has been done, utilizing a constant potential electroreductive-trimethylsilylation technique.184 The corresponding a-(trimethylsilyl)benzyl-amines were obtained in yields that depended on the nature of the substituents at nitrogen. 

The most systematically investigated acyl anion equivalents have been the IMS ethers of aromatic and heteroaromatic aldehyde cyanohydrins, TBDMS-protected cyanohydrins, - benzoyl-protected cyanohydrins, alkoxycaibonyl-protected cyanohydrins, THP-protected cyanohydrins, ethoxyethyl-protect cyanohydrins, a-(dialkylamino)nitriles, cyanophosphates, diethyl l-(trimethylsiloxy)-phenyimethyl phosphonate and dithioacetals. Deprotonation di these masked acyl anions under the action of strong basie, usually LDA, followed by treatment with a wide varies of electrophiles is of great synthetic value. If the electrophUe is another aldehyde, a-hydroxy ketones or benzoins are formed. More recently, the acyl caibanion equivalents formed by electroreduction of oxazolium salts were found to be useful for the formation of ketones, aldehydes or a-hydroxy ketones (Scheme 4). a-Methoxyvinyl-lithium also can act as an acyl anion equivalent and can be used for the formation of a-hydroxy ketones, a-diketones, ketones, y-diketones and silyl ketones. - - ... 

The electroreduction of silicon derivatives has to be focused on organylchlorosi-lanes, which usually consist of a Si—Cl bond cleavage resulting in silyl anionic... 

Finally, let us note that the electroreduction of trimethylarylsilanes themselves leads to silylated products with the loss of aromaticity [124]. 

Electroreduction of 1,3,5-tricyanobenzene was studied. When 1,3,5-tricyanobenzene was reacted with silyl and germyl radicals, 1,3,5-tricyanocyclohexadienyl radicals were obtained and detected by ESR spectroscopy. A charge-transfer complex of 1,3,5-tricyanobenzene with l,3,5-tris(dimethylamino)benzene was reported. Small amounts of isomeric tricyanobenzenes have been obtained by photochemical cycloaddition reactions ... 

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