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

doi:10.1016/0022-328X(89)85379-3

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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45 Scopus citations

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 language	English
Pages (from-to)	147-155
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	361
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(89)85379-3
State	Published - 14 Feb 1989
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Kalikhman, I. D., Albanov, A. I., Bannikova, O. B., Belousova, L. I., Voronkov, M. G., Pestunovich, V. A., Shipov, A. G., Kramarova, E. P., & Baukov, Y. I. (1989). 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. Journal of Organometallic Chemistry, 361(2), 147-155. https://doi.org/10.1016/0022-328X(89)85379-3

Kalikhman, I. D. ; Albanov, A. I. ; Bannikova, O. B. et al. / 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. In: Journal of Organometallic Chemistry. 1989 ; Vol. 361, No. 2. pp. 147-155.

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title = "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",

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).",

author = "Kalikhman, {I. D.} and Albanov, {A. I.} and Bannikova, {O. B.} and Belousova, {L. I.} and Voronkov, {M. G.} and Pestunovich, {V. A.} and Shipov, {A. G.} and Kramarova, {E. P.} and Baukov, {Yu I.}",

year = "1989",

month = feb,

day = "14",

doi = "10.1016/0022-328X(89)85379-3",

language = "English",

volume = "361",

pages = "147--155",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "2",

}

Kalikhman, ID, Albanov, AI, Bannikova, OB, Belousova, LI, Voronkov, MG, Pestunovich, VA, Shipov, AG, Kramarova, EP & Baukov, YI 1989, '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', Journal of Organometallic Chemistry, vol. 361, no. 2, pp. 147-155. https://doi.org/10.1016/0022-328X(89)85379-3

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. / Kalikhman, I. D.; Albanov, A. I.; Bannikova, O. B. et al.
In: Journal of Organometallic Chemistry, Vol. 361, No. 2, 14.02.1989, p. 147-155.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Kalikhman, I. D.

AU - Albanov, A. I.

AU - Bannikova, O. B.

AU - Belousova, L. I.

AU - Voronkov, M. G.

AU - Pestunovich, V. A.

AU - Shipov, A. G.

AU - Kramarova, E. P.

AU - Baukov, Yu I.

PY - 1989/2/14

Y1 - 1989/2/14

N2 - 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).

AB - 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).

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U2 - 10.1016/0022-328X(89)85379-3

DO - 10.1016/0022-328X(89)85379-3

M3 - Article

AN - SCOPUS:0009299606

SN - 0022-328X

VL - 361

SP - 147

EP - 155

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -

Kalikhman ID, Albanov AI, Bannikova OB, Belousova LI, Voronkov MG, Pestunovich VA et al. 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. Journal of Organometallic Chemistry. 1989 Feb 14;361(2):147-155. doi: 10.1016/0022-328X(89)85379-3

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

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