• Reagent for the formation of O-TMS cyanohydrins from carbonyl compounds.
• Tertiary alkyl halides normally undergo elimination when treated with alkali cyanides, but can be converted to the corresponding nitriles by reaction with TMSCN in the presence of SnCl4: Angew. Chem. Int. Ed., 20, 1017 (1981).
• Reacts with epoxides in the presence of ZnI2 to give trans-ɑ-siloxy isocyanides, which can be readily hydrolyzed to the hydroxy isocyanides: J. Am. Chem. Soc., 104, 5849 (1982); Org. Synth. Coll., 7, 294 (1990). In the presence of Ag salts (AgClO4, AgBF4 or AgOTf), alkenes can be converted to isocyanides in Markovnikov fashion: Synlett, 288 (1999).
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The ZnI2-catalyzed procedure allows cyanohydrins of unreactive ketones to be prepared in good yield, avoiding the unfavourable equilibria often encountered with the classical alkali cyanide method. For details and list of examples, see: Org. Synth. Coll., 7, 20 (1990). Other catalysts including Et3N or Bu3P are also effective: Chem. Lett., 537, 541 (1991). For catalysis by Methyl triphenylphosphonium iodide, A15644, see: Tetrahedron Lett., 44, 6157 (2003). In the absence of a catalyst, aldehydes have been found to give good yields of the TMS cyanohydrin, but reaction with ketones is very slow: J. Chem. Soc., Perkin 1, 2383 (1995). For use of Tetracyanoethylene, A13945, as a c-acid catalyst for both aldehydes and ketones, see: J. Chem. Soc., Perkin 1, 2155 (1995). Under the same conditions, dimethyl acetals give O-methyl cyanohydrins.• For use in asymmetric Strecker synthesis of chiral amino acids, see: Tetrahedron Lett., 29, 4397 (1988).
• For a brief survey of uses of this reagent in synthesis, see: Synlett, 1625 (2007).
• For examples of transformations of ketone TMS cyanohydrins, see: Chem. Pharm. Bull., 43, 1294 (1995).
有毒 (T)
易燃性 (F)
剧毒 (T+)
环境危害性 (N)
