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

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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.
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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.

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