Trimethylsilyl cyanide isocyanide synthesis

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. 

In addition to its use in the preparation of nitriles, trimethylsilyl cyanide (TMS-CN) is also becoming a very useful reagent for the preparation of isocyanides. 1-Chloroadamantane, for instance, gives rise to 78% of the corresponding isonitrile in the presence of catalytic amounts of TiCU (Scheme 26). Of special interest is the remarkably regioselective and stereoselective synthesis of trimethylsilyloxyalkyl isocyanides (Scheme 26) from oxiranes and TMS-CN in the presence of, for example, zinc halides (see also Section 1.8.1.3). < ... 

Regiospecific nucleophilic ring opening of oxetanes to 3-silyl-oxyisocyanides with trimethylsilyl cyanide/Znl2 in dichloromethane has been reported, and this has led to the synthesis of amino-alcohols by hydrolysis of the isocyanide group. ... 

The chemistry of trimethylsilyl cyanide continues to feature in the literature, and the first of several examples described this year is the opening of epoxides to produce P-hydroxy-isocyanides, a reaction which provides entry to a general synthesis of oxazolines and P-amino-alcohols. By using the modified conditions outlined in Scheme 20 it is possible to prepare phenylacetic acids from aryl ketones in moderate to good yield by the MeaSiCN route. ... 

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