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Synthesis of β-D galactopyranosyl amino-(N-salicylidene) - 2, 3, 4, 6-tetra-O-acetate as a new chiral Schiff base for asymmetric transformations
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Synthesis of N-(2-hydroxy-3-methoxybenzylidene) - 2, 3, 4, 6-tetra-O-acetyl -β-D galactopyranosylamine as a new chiral Schiff base for asymmetric [2+2] cycloadditions

Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, Iran
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Author to whom correspondence should be addressed.
Molbank 2005, 2005(4), M436; https://doi.org/10.3390/M436
Received: 2 June 2005 / Accepted: 22 September 2005 / Published: 1 October 2005
The importance of carbohydrates for asymmetric synthesis is well recognized [1,2,3,4].The reason that carbohydrates contain too many chiral centers and functional groups has limited their research about stereodifferentiating selection processes in asymmetric synthesis for a long time. During the past decades few carbohydrates have received increasing attention as stereodifferentiating auxiliaries in stereoselective syntheses [5]. Carbohydrates have been applied for stereo- and regioselective chemical reactions for last two decades. They could be used for biological recognition on membrane, and they play a prominent role in numerous biological processes such as tumor-cell growth [6], bacterial and viral infection or inhibition of glycosidases [2,7,8,9]. Glycosylamines are valuable intermediates in the preparation of nucleosides and drugs [10,11,12]. It has been proposed that when the Schiff base is derived from an optically active amine and an achiral aldehyde, the degree of distereoselectivity in the [2+2] cycloaddition varies [13,14]. The asymmetric Staudinger reaction utilizing 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosylamine and 2,3,4,6-tetra-O-pivaloyl-β-D-galactopyranosylamine as the chiral auxiliary in the synthesis of 2-azetidinones has been reported by us and others [15,16,17,18]. We now report compound 6 as a new chiral auxiliary Schiff base for β-lactam syntheses.
Molbank 2005 m436 i001
D-(+)-Glucose 1 was converted to 2, 3, 4, 6-tetra-O-acetyl-β-D-galactopyranosylbromide 2 by a reported method [18]. Treatment of 2 with NaN3 in 9:1 aceton-water afforded galactosylazide 3 in 95% yield. Reduction of 3 by hydrogenation in the presence of Raney Ni gave 2, 3, 4, 6-tetra-O-acetyl-β-D-galactopyranosylamine as a white solid which was recrystallized from ethanol. o-Vanillin 5 (0.87 g, 5.71 mmol) was added to a solution of 2,3,4,6-tetra-O-acetyl-β-D-galactosylamine 4 (2.00 g, 5.76 mmol) in ethanol (35 ml). The mixture was refluxed for 5 h. The resulting yellow solid N-(2-hydroxy-3-methoxybenzylidene) - 2,3,4,6-tetra-O-acetyl -β-D galactopyranosylamine 6 was collected in 90% yield by filtration.
[ α ] D 22 = + 24.5 (c = 0.02, CHCl3)
Melting point: 180-182 °C.
IR (KBr, cm-1): 3357.8-3620.1 (OH); 1743.5 (C=O); 1633.6 (C=N) cm-1.
1H-NMR (250MHz, DMSO-d6): δ= 12.44 (OH, br, 1H); 8.53 (NCH, s, 1H); 7.30-6.82 (Ar-H, m, 4H); 3.84 (OCH3, s, 3H); 1.91-2.10 (4CH3CO, s, 12H),
13C-NMR (62.9 MHz, DMSO-d6): δ= 170.82-165.03 (C=O); 124.90-115.21 (Ar); 21.10-20.97(OCH3).
MS (m⁄z, %): 481 (2.00); 331 (2.10); 169 (21.60); 109 (18.10); 43 (100.00).

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

Acknowledgment

The authors thank the Shiraz University Research Council for financial support (Grant No. 83-GR-SC-31 and 84-GR-SC-23).

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