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Synlett 2006(15): 2498-2500  
DOI: 10.1055/s-2006-950401
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Simple and Efficient Synthesis of 2-Deoxy-l-ribose from 2-Deoxy-d-ribose

Qi Ji, Meili Pang, Jie Han, Suihan Feng, Xiaotian Zhang, Yuxin Ma, Jiben Meng*
Department of Chemistry, Nankai University, Tianjin 300071, P. R. of China
Fax: +86(22)23502230; e-Mail: mengjiben@nankai.edu.cn;
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Publication History

Received 15 May 2006
Publication Date:
08 September 2006 (online)

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Abstract

An efficient synthesis of 2-deoxy-l-ribose was achieved without chromatography starting from its enantiomer 2-deoxy-d-ribose in more than 30% overall yield. An unexpected product, 2-deoxy-xylose, was obtained under slightly different reaction conditions and isolated with partial racemization. The structure of the scalemic 2-deoxy-xylose was confirmed by X-ray crystallography.

Key words

synthesis - deoxyribose - enantiomer

8

Typical procedure for 2-deoxy-xylose: To a solution of 4 (10 g, 0.022 mol) in DMF (30 mL) was added potassium benzoate (30 g, 0.19 mol), and the mixture was heated at reflux with stirring for 10 h. The resulting mixture was concentrated and stirred with H2O (50 mL) and CH2Cl2 (30 mL), filtered, and the aqueous layer of the filtrate was separated and extracted with CH2Cl2 (30 mL). The combined organic layers were evaporated to dryness and the residue recrystallized from EtOH-H2O to give 7 as white crystals (3.9 g, 50%). This material was dissolved in MeOH (60 mL), the solution was saturated with NH3, and stirred at r.t. for 24 h. After evaporation, the residual syrup was partitioned between H2O (70 mL) and CH2Cl2 (70 mL), and the aqueous layer was separated and washed again with CH2Cl2 (50 mL). The resulting aqueous solution was saturated with benzoic acid and heated at reflux for 1 h. After cooling to r.t., CHCl3 (25 mL) was added, and the aqueous layer separated and washed again with CHCl3 (25 mL). The aqueous layer was concentrated to dryness and recrystallized from acetone-EtOAc (1:1) to give 2-deoxy-xylose (9) as white crystals (1.6 g, 83%). Single crystals suitable for X-ray diffraction measurements were obtained from acetone-EtOAc by slow evaporation at r.t. Analytical data: mp 77-78 °C; [α]20 D +0.6 (c 1.00, H2O); 1H NMR (300 MHz, DMSO-d 6): δ = 6.47 (d, J = 6.6 Hz, 1 H), 4.84 (dd, J 1 = 4.6 Hz, J 2 = 4.8 Hz, 2 H), 4.59-4.53 (m, 1 H), 3.68-3.62 (dd, J 1 = J 2 = 5.0 Hz, 1 H), 3.33-3.27 (m, 1 H), 3.19-3.10 (m, 1 H), 2.98-2.91 (m, 1H), 1.93-1.87 (dddd, J 1 = J 2 = J 3 = J 4 = 2.0 Hz, 1 H), 1.31-1.20 (m, 1 H); ESI-MS: m/z = 179 [M + HCOO-]; Anal. Calcd for C5H10O4: C, 44.77; H, 7.52. Found: C, 45.02; H, 7.33.

10

CCDC 293775 contains the supplementary crystallographic data and collection parameters for 9. These data can be obtained free of charge via ww.ccdc.cam.ac.uk/conts/retrieving.html.

11

Typical procedure for 2-deoxy-l-ribose: To a solution of 4 (10 g, 0.022 mol) in DMF (30 mL) was added H2O (5 mL) and potassium benzoate (25 g, 0.16 mol), and the mixture was heated at reflux with stirring for 6 h. The resulting mixture was concentrated and stirred with H2O (50 mL) and CH2Cl2 (30 mL), filtered, and the aqueous layer of the filtrate was separated and extracted with CH2Cl2 (30 mL). The organic layers were combined and treated with Na2CO3 and evaporated to a syrup (mixture 10). This material was dissolved in MeOH (60 mL), the solution saturated with NH3, and stirred at r.t. for 24 h. After evaporation, the residual syrup was partitioned between H2O (20 mL) and CH2Cl2 (20 mL), and the aqueous layer was separated and washed again with CH2Cl2 (20 mL) before being evaporated to dryness and the residue recrystallized from Et2O to give mixture 11 as a white solid (1.9 g, 46%). The solid was heated at reflux in a saturated aqueous solution of benzoic acid (80 mL) for 1 h. After cooling to r.t., CHCl3 (30 mL) was added, and the aqueous layer separated and washed again with CHCl3 (20 mL) before being concentrated to give a colorless syrup. The syrup was treated with a small amount of acetone-isopropanol (7:1) and refrigerated for about a week to give 2-deoxy-l-ribose (12) as a white powder (1.6 g, 95%). Data: mp 74-76 °C; [α]20 D +53 (c 1.00, H2O); 1H NMR (300 MHz, D2O): δ = 5.47-5.13 (m, 1 H), 4.22-3.42 (m, 4 H), 2.29-1.50 (m, 2 H); ESI-MS: m/z = 179 [M+HCOO-] (weak); Anal. Calcd for C5H10O4: C, 44.77; H, 7.52. Found: C, 44.61; H, 7.75.