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

I. D. Kalikhman, A. I. Albanov, O. B. Bannikova, L. I. Belousova, M. G. Voronkov, V. A. Pestunovich, A. G. Shipov, E. P. Kramarova, Yu I. Baukov

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Abstract

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 ClSiN bond. The already known products, (OSi) 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).

Original languageEnglish
Pages (from-to)147-155
Number of pages9
JournalJournal of Organometallic Chemistry
Volume361
Issue number2
DOIs
StatePublished - 14 Feb 1989
Externally publishedYes

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