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

1989; Elsevier BV; Volume: 361; Issue: 2 Linguagem: Inglês

10.1016/0022-328x(89)85379-3

1872-8561

I. D. Kalikhman, А. И. Албанов, O. B. BANNIKOVA, L. I. Belousova, М. Г. Воронков, V. A. Pestunovich, А.Г. Шипов, Е.П. Крамарова, YU. I. BAUKOV,

Coordination Chemistry and Organometallics

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-[dimethyl(chloromethyl)silyl]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 thermodynamic control. The same compounds are also formed via the Chapman rearrangement of the intermediates (IV).