2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes

Alexander A. Tishkov, Alexey V. Lesiv, Yulya A. Khomutova, Yury A. Strelenko, Ivan D. Nesterov, Michael Yu Antipin, Sema L. Ioffe, Scott E Denmark

Research output: Contribution to journalArticle

Abstract

3-Alkyl-substituted 1,2-oxazine N-oxides 2 can be selectively transformed into 2-silyloxy-1,2-oxazines 1 upon treatment with silylating reagents. In the solid state derivatives 1 adopt a chair conformation with the pyramidal nitrogen atom, whereas in solution they exist as an equilibrating mixture of two conformers (ΔG† 55-60 kJ/mol). A preliminary study of the reactivity of nitrosals 1 has shown that they react with O- and N-stabilized carbocations to yield 1,2-oxazine N-oxides with a functionalized alkyl substituent at the 3-position. Moreover, compounds 1 can rearrange into silyloxy-1,2-oxazines 5 and react with morpholine to produce 3-morpholinoalkyl-1,2-oxazines 7 existing in a tautameric equilibrium with open-chain oximes 6.

Original languageEnglish (US)
Pages (from-to)9477-9480
Number of pages4
JournalJournal of Organic Chemistry
Volume68
Issue number24
DOIs
StatePublished - Nov 28 2003

Fingerprint

Oxazines
Acetals
Alkenes
Oxides
Oximes
Conformations
Nitrogen
Derivatives
Atoms

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Tishkov, A. A., Lesiv, A. V., Khomutova, Y. A., Strelenko, Y. A., Nesterov, I. D., Antipin, M. Y., ... Denmark, S. E. (2003). 2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes. Journal of Organic Chemistry, 68(24), 9477-9480. https://doi.org/10.1021/jo034669a

2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes. / Tishkov, Alexander A.; Lesiv, Alexey V.; Khomutova, Yulya A.; Strelenko, Yury A.; Nesterov, Ivan D.; Antipin, Michael Yu; Ioffe, Sema L.; Denmark, Scott E.

In: Journal of Organic Chemistry, Vol. 68, No. 24, 28.11.2003, p. 9477-9480.

Research output: Contribution to journalArticle

Tishkov, AA, Lesiv, AV, Khomutova, YA, Strelenko, YA, Nesterov, ID, Antipin, MY, Ioffe, SL & Denmark, SE 2003, '2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes', Journal of Organic Chemistry, vol. 68, no. 24, pp. 9477-9480. https://doi.org/10.1021/jo034669a
Tishkov AA, Lesiv AV, Khomutova YA, Strelenko YA, Nesterov ID, Antipin MY et al. 2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes. Journal of Organic Chemistry. 2003 Nov 28;68(24):9477-9480. https://doi.org/10.1021/jo034669a
Tishkov, Alexander A. ; Lesiv, Alexey V. ; Khomutova, Yulya A. ; Strelenko, Yury A. ; Nesterov, Ivan D. ; Antipin, Michael Yu ; Ioffe, Sema L. ; Denmark, Scott E. / 2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes. In: Journal of Organic Chemistry. 2003 ; Vol. 68, No. 24. pp. 9477-9480.
@article{4dee85090ed547298594d20c4f453b7f,
title = "2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes",
abstract = "3-Alkyl-substituted 1,2-oxazine N-oxides 2 can be selectively transformed into 2-silyloxy-1,2-oxazines 1 upon treatment with silylating reagents. In the solid state derivatives 1 adopt a chair conformation with the pyramidal nitrogen atom, whereas in solution they exist as an equilibrating mixture of two conformers (ΔG† 55-60 kJ/mol). A preliminary study of the reactivity of nitrosals 1 has shown that they react with O- and N-stabilized carbocations to yield 1,2-oxazine N-oxides with a functionalized alkyl substituent at the 3-position. Moreover, compounds 1 can rearrange into silyloxy-1,2-oxazines 5 and react with morpholine to produce 3-morpholinoalkyl-1,2-oxazines 7 existing in a tautameric equilibrium with open-chain oximes 6.",
author = "Tishkov, {Alexander A.} and Lesiv, {Alexey V.} and Khomutova, {Yulya A.} and Strelenko, {Yury A.} and Nesterov, {Ivan D.} and Antipin, {Michael Yu} and Ioffe, {Sema L.} and Denmark, {Scott E}",
year = "2003",
month = "11",
day = "28",
doi = "10.1021/jo034669a",
language = "English (US)",
volume = "68",
pages = "9477--9480",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - 2-Silyloxy-1,2-oxazines, a New Type of Acetals of Conjugated Nitroso Alkenes

AU - Tishkov, Alexander A.

AU - Lesiv, Alexey V.

AU - Khomutova, Yulya A.

AU - Strelenko, Yury A.

AU - Nesterov, Ivan D.

AU - Antipin, Michael Yu

AU - Ioffe, Sema L.

AU - Denmark, Scott E

PY - 2003/11/28

Y1 - 2003/11/28

N2 - 3-Alkyl-substituted 1,2-oxazine N-oxides 2 can be selectively transformed into 2-silyloxy-1,2-oxazines 1 upon treatment with silylating reagents. In the solid state derivatives 1 adopt a chair conformation with the pyramidal nitrogen atom, whereas in solution they exist as an equilibrating mixture of two conformers (ΔG† 55-60 kJ/mol). A preliminary study of the reactivity of nitrosals 1 has shown that they react with O- and N-stabilized carbocations to yield 1,2-oxazine N-oxides with a functionalized alkyl substituent at the 3-position. Moreover, compounds 1 can rearrange into silyloxy-1,2-oxazines 5 and react with morpholine to produce 3-morpholinoalkyl-1,2-oxazines 7 existing in a tautameric equilibrium with open-chain oximes 6.

AB - 3-Alkyl-substituted 1,2-oxazine N-oxides 2 can be selectively transformed into 2-silyloxy-1,2-oxazines 1 upon treatment with silylating reagents. In the solid state derivatives 1 adopt a chair conformation with the pyramidal nitrogen atom, whereas in solution they exist as an equilibrating mixture of two conformers (ΔG† 55-60 kJ/mol). A preliminary study of the reactivity of nitrosals 1 has shown that they react with O- and N-stabilized carbocations to yield 1,2-oxazine N-oxides with a functionalized alkyl substituent at the 3-position. Moreover, compounds 1 can rearrange into silyloxy-1,2-oxazines 5 and react with morpholine to produce 3-morpholinoalkyl-1,2-oxazines 7 existing in a tautameric equilibrium with open-chain oximes 6.

UR - http://www.scopus.com/inward/record.url?scp=0344391947&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0344391947&partnerID=8YFLogxK

U2 - 10.1021/jo034669a

DO - 10.1021/jo034669a

M3 - Article

C2 - 14629175

AN - SCOPUS:0344391947

VL - 68

SP - 9477

EP - 9480

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 24

ER -