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Synthesis 2011(1): 109-118  
DOI: 10.1055/s-0030-1258326
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

β-Alkoxy-γ-amino Aldehydes by Internal Redox Ring Cleavages of Carbohydrate-Derived Enantiopure 1,2-Oxazines and Preparation of Heterocycles with Aminopolyol Side Chain

Ahmed Al-Harrasia,b, Léa Bouchéa, Reinhold Zimmera, Hans-Ulrich Reissig*a
a Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany
Fax: +49(30)83855367; e-Mail: hans.reissig@chemie.fu-berlin.de;
b University of Nizwa, College of Arts and Sciences, Department of Biological Sciences and Chemistry, P.O Box 33, Postal Code 616, Birkat Al Mauz, Nizwa, Sultanate of Oman
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Publikationsverlauf

Received 7 September 2010
Publikationsdatum:
15. November 2010 (online)

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Abstract

N-Methylation of syn- or anti-configured 3,6-dihydro-2H-1,2-oxazines and subsequent treatment with triethylamine smoothly provided enantiopure α,β-unsaturated β-alkoxy-γ-amino aldehydes bearing different protected diol, triol, or tetrol side chains in good to excellent yields. The N-O bond cleavage occurs under mild conditions and involves an internal redox process. The method is also applicable to tetrahydro-2H-1,2-oxazines, which either lead to 4-amino ketose or aldose derivatives (d-sorbose or d-idose configuration). The equivalency of the generated β-alkoxyenal moiety with 1,3-dicarbonyl compounds could be demonstrated by condensation reactions with hydrazine or 2-aminoimidazole derivatives providing a series of new pyrazole or imidazo[1,2-a]pyrimidine derivatives with stereodefined and protected aminopolyol side chains.

Key words

carbohydrates - 1,2-oxazines - alkylation - aldehydes - pyrazoles - imidazo[1,2-a]pyrimidines

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Compound 16 was prepared by Grignard reaction of the corresponding 4-oxo-1,2-oxazine of 16 with MeMgBr: Hyrosová, E.; Reissig, H.-U., unpublished results.