Synlett 2002(10): 1715-1717
DOI: 10.1055/s-2002-34222
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 4-Carbamoyl-2-oxazolidinones C-4-Linked with a Saccharide Moiety via Bucherer-Bergs Reaction of Hexofuranos-5-uloses

Júlia Mičováa, Bohumil Steinera, Miroslav Koóš*a, Vratislav Langerb, Dalma Gyepesovác
a Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84238 Bratislava, Slovakia
Fax: +421(2)59410222; e-Mail: chemmiro@savba.sk;
b Department of Inorganic Environmental Chemistry, Chalmers University of Technology, SE-41296 Gothenburg, Sweden
c Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-84236 Bratislava, Slovakia
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Publikationsverlauf

Received 20 June 2002
Publikationsdatum:
23. September 2002 (online)

Abstract

Application of the Bucherer-Bergs reaction to 6-O-unprotected hexofuranos-5-uloses led to the formation of 4-carbamoyl-2-oxazolidinones C-4-linked with a carbohydrate moiety instead of expected carbohydrate-C-5-linked hydantoin (imidazolidin-2,4-dione) derivatives. Starting from hexofuranos-5-uloses having all hydroxyl groups suitably protected, only corresponding saccharide-linked hydandoins were obtained.

    References

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6

Recently, we have prepared both 5-(R)- and 5-(S)-hydantoins 11 and 12 by selective detritylation of 5 and 6, respectively. These were fully characterized by 1H and
13C NMR and mass spectral data and at present, they are subjected to X-ray analysis to determine the configuration at C-5.

12

In a typical experimental procedure, a mixture of 5-ulose 3 (10 mmol), KCN (20 mmol), and (NH4)2CO3 in 50% aq EtOH (20 mL) was stirred at 60 °C for 8 h. Ethanol was then evaporated and the product extracted with CHCl3. After complete solvent removal in vacuo, the residue was chromatographed on a column of silica gel using 8:1 (v/v) CHCl3-MeOH as an eluent. This afforded 4 (43% yield) which was crystallized from EtOAc: mp 235-237 °C; [α]D +58 (c 1, MeOH); 1H NMR (300 MHz, CDCl3): δ = 6.80
(br s, 1 H, NH), 6.09 (br s, 1 H, NH), 5.67 (br s, 1 H, NH), 4.98 (s, 1 H, H-1), 4.82 (dd, 1 H, J 2,3 = 5.9 Hz, J 3,4 = 3.4 Hz, H-3), 4.57 (d, 1 H, J 5 a,5 b = 7.1 Hz, H-5′a), 4.56 (d, 1 H, H-2), 4.46 (d, 1 H, H-5′b), 4.45 (d, 1 H, H-4), 3.35 (s, 3 H, OCH3), 1.54 and 1.28 (2 s, each 3 H, Me2C); 13C NMR (75.5 MHz, CDCl3):
δ = 172.9 (CONH2), 159.1 (NHCOO), 113.2 (CMe2), 106.9 (C-1), 85.1 (C-2), 79.9 (C-3), 78.6 (C-4), 72.6 (C-5′), 64.0 (C-4′ = C-5), 55.0 (OCH3), 25.8 and 23.9 [(CH3)2C] (data for the 2-oxazolidinone moiety are identified by a prime); MS (EI, 70 eV): m/z (%) = 287 [M - Me]+, 258 (100) [M - CONH2]+, 226, 170, 134, 75, 40; CIMS: m/z 382 [M + 80]+. Anal. Calcd for C12H18N2O7: C, 47.70; H, 6.00; N, 9.27. Found: C, 47.81; H, 6.08; N, 9.20. The 2-oxazolidinone derivatives 7-10 were prepared analogously (yield: 7, 38%; 8, 45%; 9, 41%; 10, 44%), starting from the corresponding 5-uloses.

14

Crystallographic data for 4 has been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 178704. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk).