The reaction of N-trimethylsilyl-amides and lactams with dimethyl(chloromethyl)chlorosilane. Kinetically controlled formation of (N-Si) chelate intermediates, O-imidates and their reaarangement to final (O-Si) chelate N-amides...

Article abstract of DOI:10.1016/0022-328X(89)85379-3

The multistage character of the reaction of dimethyl(chloromethyl)chlorosilane (I) with N-trimethylsilyl-amides and -lactams (II) was shown by NMR monitoring.Interaction of the reactants starts with transsilylation, leading to Me3SiCl and the corresponding N-amide or-lactam (III).The second stage, intramolecular (dimethylchlorosilyl)methylation of unstable III, proceeds in two directions.A kinetically controlled transformation of III affords previously unknown O-(dimethylchlorosilyl)methylated intermediates, O-<(dimethylchlorosilyl)methyl>imidates (IV) containing a hypervalent Cl-Si-N bond.The already known products (O-Si) chelate N-(dimethylchlorosilyl)methyl>amides (V), arise from the reaction carried out under thermodinamic control.The same compounds are also formed via the Chapman rearrangement of the intermediates (IV).