The Use of Silylation in Organic Syntheses
The Use of Silylation in Organic Syntheses
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硅烷化在有机合成中的应用
DOI：
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发表时间：
1965
期刊：
影响因子：
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通讯作者：
A. Ritter
中科院分区：
文献类型：
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作者：
L. Birkofer;A. Ritter
术语甲硅烷基化用于表示将三有机甲硅烷基部分，特别是三甲基甲硅烷基物质引入有机化合物中。- 甲硅烷基化的氨基酸和糖分别特别适合于肽和糖的合成，因为甲硅烷基基团可以在温和条件下容易地裂解。许多二胺仅在甲硅烷基化后才进行闭环，例如用光气。- O-甲硅烷基化的内酰亚胺醚（即环状亚氨基醚）通过烷基卤化物转化为N-烷基衍生物。具有强极化SiC键的化合物可用于扩链。卤代脂肪酸的甲硅烷基酯与氰酸银生成内酯。- 三甲基甲硅烷基叠氮化物是非常热稳定的，并且表现得像有机叠氮化物。它与炔属化合物、三烷基膦和三芳基膦反应，分别得到甲硅烷基化的三唑衍生物、三烷基膦N-甲硅烷基亚胺和三芳基膦，分别得到甲硅烷基化的三唑衍生物、三烷基膦N-甲硅烷基亚胺和三芳基膦N-甲硅烷基亚胺，其中甲硅烷基可以在温和条件下除去。
The term silylation is used to denote the introduction of a triorganosilyl moiety, especially the trimethylsilyl species, into organic compounds. - Silylated amino acids and sugars are particularly suitable for the syntheses of peptides and saccharides, respectively, since the silyl group can be cleaved off readily under mild conditions. Many diamines undergo ring closure, e.g. with phosgene, only after silylation. - O-silylated lactim ethers (i.e. cyclic imino ethers) are converted into N-alkyl derivatives by alkyl halides. Compounds with a strongly polarized SiC bond may be used for chain extension. Silyl esters of halogeno fatty acids yield lactones with silver cyanate. - Trimethylsilyl azide is thermally very stable and behaves like organic azides. It reacts with acetylenic compounds, trialkylphosphines, and triarylphosphines to yield silylated triazole derivatives, trialkylphosphines N-silylimines, and triarylphosphines to yield silylated triazole dervatives, trialkylphosphine N-silylimines, and triarylphosphine N-silylimines, respectively, from which the silyl groups can be removed under mild conditions.