No abstract

No abstract

Trimethylsilylmethyl isothiocyanate (I) reacts consecutively with the Grignard compounds (II) and the halides (III) to form the thioimidates (IV).

N-(Silylmethyl)imines generate N-protonated azomethine ylides of nonstabilized type when treated with water in HMPA, which undergo stereospecific and regioselective cycloadditions with electron-poor olefins affording N-unsubstituted pyrrolidines. On the other hand, fluoride-induced desilylation of the imines leads to 2-azaallyl anions which are found to be synthetic equivalents of aminomethyl anion in the Michael additions with electron-poor olefins and nucleophilic additions with carbonyl compounds.

The reactions of ((trimethylsilyl)methyl)iminotriphenylphosphorane, prepared in situ from (trimethylsilyl)methyl azide and triphenylphosphine, with carbonyl compounds and with heterocumulenes such as carbon dioxide, carbon disulfide, isocyanates, isothiocyanates, and a ketene provide convenient one-pot syntheses of the corresponding N-((trimethylsilyl)methyl)imines and (trimethylsilyl)methyl-substituted heterocumulenes, which are versatile