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

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

47 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 B.V.",

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).

UR - https://www.scopus.com/pages/publications/0009299606

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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