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Synthesis 2004(8): 1159-1170  
DOI: 10.1055/s-2004-822346
PAPER
© Georg Thieme Verlag Stuttgart · New York

A Convenient Procedure for the Synthesis of Substituted 3-α-Haloalkyl-5,6-dihydro-4H-1,2-oxazines

Michael S. Klenov, Alexey V. Lesiv*, Yulya A. Khomutova, Ivan D. Nesterov, Sema L. Ioffe*
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, Moscow, Leninsky prosp. 47, Russian Federation
Fax: +7(095)1355328; e-Mail: iof@ioc.ac.ru;
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Publication History

Received 9 February 2004
Publication Date:
28 April 2004 (online)

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Abstract

A general and convenient method for the synthesis of the scarcely known 3-α-haloalkyl-5,6-dihydro-4H-1,2-oxazines 2 via silylation of the corresponding six-membered cyclic nitronates 1 or the first obtained 2-silyloxy-1,2-oxazines 3 by Me3SiX/Et3N (X = Cl or Br) is elaborated.

Key words

aliphatic nitro compounds - 5,6-dihydro-4H-1,2-oxazine N-oxides - 2-silyloxy-1,2-oxazines - 3-α-haloalkyl-5,6-dihydro-4H-1,2-oxazines - silylation

    References

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2

Smirnov, V. O.; Ioffe, S. L.; Tishkov, A. A.; Khomutova, Y. A.; Nesterov, I. D.; Antipin, M. Y.; Smit, W. A.; Tartakovsky, V. A. Angew. Chem. submitted.

7

Although pyridine is more efficient than Et3N (see Table [2] ) it is not recommended owing to possible C-4 deprotonation (see also ref. [3] ).

10

CCDC 230282 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by e-mail to data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

14

The interaction of enamines 3 with Me3SiCN gives not oxazines 7, but leads to another product, which contains a fragment of 5-aminoizoxazole. This reaction will be discussed in our following publications.

19

NMR spectra of enamines 3d,e,i are broadened (at 300 K) due to dynamic process (for details, see Ref. [3] and our next publication).