Silylation silanol

The phosphorus ylides of the Wittig reaction can be replaced by trimethylsilylmethyl-carbanions (Peterson reaction). These silylated carbanions add to carbonyl groups and can easily be eliminated with base to give olefins. The only by-products are volatile silanols. They are more easily removed than the phosphine oxides or phosphates of the more conventional Wittig or Homer reactions (D.J. Peterson, 1968). 

Apart from the mentioned advantages, the polymeric reagents covalently adsorbed by silica also diminish its inherent non-specific adsorptivity. One of the ways to synthesize a polymeric modifier of this type is a copolymerization of a vinylsilane with a compound of the desired functionality. The segments carrying silyl groups will condense with the surface silanols forming anchors or trains . 

Prior to the chemical reaction of the silane with the silanol-groups on the sUica surface, the silane molecule has to make contact with the sUica surface by adsorption. Then the chemical reaction of silica with an alkoxy-silyl moiety of the coupling agent takes place in a two-step, endothermic reaction. The primary step is the reaction of alkoxy-groups with silanol-groups on the silica filler surface [4]. Two possible mechanisms are reported ... 

ISOC reaction was employed to synthesize substituted tetrahydrofurans 172 fused to isoxazolines (Scheme 21) [44b]. The silyl nitronates 170 resulted via the nitro ethers 169 from base-mediated Michael addition of allyl alcohols 168 to nitro olefins 167. Cycloaddition of 170 followed by elimination of silanol provided 172. Reactions were conducted in stepwise and one-pot tandem fashion (see Table 16). A terminal olefinic Me substituent increased the rate of cycloaddition (Entry 3), while an internal olefinic Me substituent decreased it (Entry 4). 

Treatment of highly sterically hindered iodosilanes with a silver salt in a solvent containing water has also been used successfully to prepare bulky silanols (Scheme 6). The introduction of the OH group seems to occur not only by hydrolysis of the silyl perchlorates formed, but also by reaction of the bridged silicocationic species that are formed as intermediates in this type of reaction (62). The reaction... 

The method most commonly used to prepare bonded phases from silica involves reaction of the silica with a substituted dimethylchlorosilane. Fig. 3.2a shows the reaction, in which HC1 is eliminated between a surface silanol group and the silylating agent. 

Before reaction, the silica is treated with acid (eg refluxed for a few hours with 0.1 mol dm-3 HC1). This treatment produces a high concentration of reactive silanol groups at the silica surface, and also removes metal contamination and fines from the pores of the material. After drying, the silica is then refluxed with the dimethylchlorosi-lane in a suitable solvent, washed free of unreacted silane and dried. This reaction produces what is called a monomeric bonded phase, as each molecule of the silylating agent can react with only one silanol group. 

Addition of a silyl substituent into a-position of the a-(benzotriazol-l-yl)alkyl ether brings additional possibilities. Thus, lithiation of silyl ether 770 followed by treatment with an aldehyde or ketone gives unstable P-hydroxy-a-silyl-a-(benzotriazol-l-yl)alkyl ether 771 that spontaneously eliminates silanol to give vinyl ether 772 (Scheme 121). Treatment with ZnBr2 followed by hydrolysis with a diluted acid removes both the benzotriazolyl and the methyl groups to furnish carboxylic acid 773. In this way, in a simple manner, aldehydes and ketones are converted to one-carbon homologated carboxylic acid <1996S1425>. 

On the basis of available experimental data, it is impossible to choose a definite pathway of elimination of silanol. However, study of silylation of methyl P -nitropropionate (411) with BSA in the presence of trapping agents rigorously proved that silyl nitronate D is initially formed. This compound can be detected in the [3 + 2]-cycloaddition reaction with methyl acrylate product (413). If silylation of AN (411) is performed in the presence of ethyl vinyl ether, a-nitrosoalkene E can be successfully trapped in as heterodiene a Diels-Alder reaction. Dihydroox-azine (414) is formed, and its silylation affords isolable product (415). 

Ketoximes and aldoximes Ketoximes and aldoximes are uniquely substituted C=N systems that react differently with titanocene and zirconocene. Aliphatic and alicyclic O-silylated ketoximes R2C=N OSiMe3 react with complex 1 with elimination of the alkyne and N—O bond cleavage to give imido-silanolates 85 [45],... 

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