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Synlett 2010(2): 271-275  
DOI: 10.1055/s-0029-1218552
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Easy Access to Configurationally Controlled C-Glycofuranoside-Based Building Blocks by Means of Formyl C-Glycofuranosides

Yolanda Vera-Ayosoa, Pastora Borracheroa, Francisca Cabrera-Escribano*a, Manuel Gómez-Guilléna, Joaquim Canerb, Jaume Farrásb
a Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, Apartado de Correos No. 1203, 41071 Sevilla, Spain
Fax: +34(95)4624960; e-Mail: fcabrera@us.es ;
b Departamento de Química Orgánica, Universidad de Barcelona, Av. Diagonal 647, 08028 Barcelona, Spain
Further Information

Publication History

Received 24 September 2009
Publication Date:
09 December 2009 (online)

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Abstract

A general approach to enantiopure C-glycofuranoside-based hybrid α/β-amino acids and nitrones, among other valuable building blocks, has been established via formyl C-glycofuranosides, easily available from hexose-derived equatorial-2-OH-glycopyranosides by DAST-promoted ring contraction.

Key words

C-glycofuranoside-based building blocks - formyl C-glycofuranosides - DAST-promoted ring contraction - C-glycofuranosyl nitrones - C-glycofuranosyl amino acids

    References and Notes

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13

Preparation and More Relevant Data of Compound 10
A soln of 9 (105 mg, 0.340 mmol) in dry THF (4.8 mL) containing 3 Å MS was treated with NaCNBH3 (273 mg, 4.35 mmol). The mixture was stirred for 15 min, and then Et2O-HCl (3.5%, 6 mL) was added. After 5 min, the reaction was diluted with H2O (20 mL) and CH2Cl2 (20 mL). After separation, the organic layer was successively washed with sat. aq NaHCO3 (50 mL) and brine (50 mL), dried (Na2SO4), and concentrated. Column chromatography (hexane-EtOAc, 3:1) gave pure 10 (64 mg, 64%).
Analytical Data
[α]D ²4 +16.2 (c 0.63, CH2Cl2). IR: νmax = 2108 (N3) cm-¹. ¹H NMR (500 MHz, acetone-d 6): δ = 7.36-7.26 (m, 5 H, Ph), 4.75 (s br, 1 H, OHC4), 4.55 (s, 2 H, CH2Ph), 4.55-4.53 (m, 1 H, H-4), 4.17 (ddd, 1 H, J 1,2 = J 1 ′ ,2 = 5.7 Hz, J 2,3 = 3.7 Hz, H-2), 4.14 (dd, 1 H, J 3,4 = 4.2 Hz, H-3), 3.93 (ddd, 1 H, J 4,5 = 7.5 Hz, J 5,6 ′ = 4.5 Hz, J 5,6 = 3.0 Hz, H-5), 3.65 (dd, 1 H, J 6,6 ′ = 11.0 Hz, H-6), 3.58 (dd, 1 H, H-6′), 3.56 (dd, 1 H, J 1,1 ′ = 10.0 Hz, H-1), 3.43 (dd, 1 H, H-1′), 3.31 (s, 3H, OCH3) ppm. HRMS (CI): m/z calcd for C14H19N3O4 + H: 294.1454; found: 294.1462.

16

The ratio of 24/25 was calculated by the ¹H NMR (CDCl3) of the mixture, in particular from the signals of H-4 of both stereoisomers: δ = 5.65 ppm (dd, 1 H, J 4,5 = 7.8 Hz, J 3,4 = 4.5 Hz, H-4) observed for the major stereoisomer 24, and that observed at δ = 4.80 ppm (dd, 1 H, J 4,5 = 7.2 Hz, J 3,4 = 4.8 Hz, H-4) for 25.

18

More Relevant Data Compound 16: [α]D ²¹ +37 (c 0.77, acetone). ¹H NMR (500 MHz, acetone-d 6): δ = 7.36-7.33 (m, 5 H, Ph), 7.09 (d, 1 H, J NH,3 = 7.0 Hz, CCONH), 6.43 (s br, 1 H, OCONH), 4.58-4.53 (m, 1 H, H-3), 4.57 and 4.58 (each 2 d, 1 H, J H,H ′ = 12.9 Hz, CH2Ph), 4.45 (d, 1 H, J OH,4 = 8.0 Hz, OHC4), 4.31 (ddd, 1 H, J 2,3 = 8.0 Hz, J 1 ′ ,2 = 4.5 Hz, J 1,2 = 3.0 Hz, H-2), 4.17-4.14 (m, 1 H, H-4), 4.01 (ddd, 1 H, J 5,6 = J 5,6 ′ = 4.0 Hz, J 4,5 = 3.0 Hz, H-5), 3.77 (dd, 1 H, J gem = 16.5 Hz, J NH,CH2a = 6.0 Hz, NHCH a 2), 3.72 (dd, 1 H, J NH,CH2b = 6.0 Hz, NHCH b 2), 3.55 (dd, 1 H, J 6,6 ′ = 10.5 Hz, H-6), 3.52 (dd, 1 H, H-6′), 3.50 (dd, 1 H, J 1,1 ′ = 10.5 Hz, H-1), 3.40 (dd, 1 H, H-1′), 3.35 (s, 3 H, OCH3), 1.43 [s, 9 H, C(CH3)3] ppm. ¹³C NMR (125.7 MHz, acetone-d 6): δ = 170.5, 157.0, 139.6-128.2, 85.2, 79.6, 78.9, 73.8, 73.1, 72.9, 72.0, 59.3, 53.9, 44.9, 28.6 ppm. HRMS (CI): m/z calcd for C21H32N2O7 + H: 425.2288; found: 425.2291. Anal. Calcd for C21H32N2O7: C, 59.42; H, 7.60; N, 6.60. Found: C, 59.12; H, 7.45; N, 6.72.
Compound 20: [α]D ²4 +52 (c 0.66, CH2Cl2). IR: νmax = 2114 (N3) cm-¹. ¹H NMR (500 MHz, CDCl3): δ = 7.07 (dd, 1 H, J NH,CH2a = 5.0 Hz, NH), 5.22 (dd, 1 H, J 4,5 = 8.5 Hz, J 3,4 = 4.5 Hz, H-4), 4.68 (dd, 1 H, J 2,3 = 4.5 Hz, H-3), 4.62 (d, 1 H, H-2), 4.40-4.36 (m, 1 H, H-5), 4.36 (dd, 1 H, J 6,6 ′ = 12.5 Hz, J 5,6 = 2.5 Hz, H-6), 4.23 (q, 2 H, J = 7.0, C2H5), 4.13 (dd, 1 H, J 5,6 ′ = 4.0 Hz, H-6′), 4.11 (dd, 1 H, J gem = 18.0 Hz, NHCH a 2), 4.07 (dd, 1 H, NHCH b 2), 2.16, 2.09 (2 s, each 3 H, COCH3), 1.29 (t, 3 H, C2H5) ppm. HRMS (CI): m/z calcd for C14H20N4O8 + H: 373.1359; found: 373.1349.
Compound 22: [α]D ²4 -1.2 (c 0.75, CH2Cl2). IR: νmax = 2112 (N3) cm-¹. ¹H NMR (500 MHz, CDCl3): δ = 7.41 (s, 5 H, Ph), 6.79 (d, 1 H, J 1,2 = 4.5 Hz, H-1), 5.20 (dd, 1 H, J 4,5 = 8.0 Hz, J 3,4 = 5.0 Hz, H-4), 5.15 (dd, 1 H, J 2,3 = 4.5 Hz, H-2), 4.94 (dd, 1 H, H-3), 4.91 (s, 2 H, CH2Ph), 4.34 (dd, 1 H, J 6,6 ′ = 12.0, J 5,6 = 3.0 Hz, H-6), 4.24 (ddd, J 5,6 ′ = 4.5 Hz, H-5), 4.04 (dd, 1 H, H-6′), 2.14, 2.08 (2 s, each 3 H, 2 COCH3) ppm. ¹³C NMR (125.7 MHz, CDCl3): δ = 170.7, 170.2, 136.2, 132.0-129.2, 77.2, 77.0, 73.5, 69.3, 63.3, 62.7, 20.9, 20.4 ppm. HRMS (CI): m/z calcd for C17H20N4O6 + H: 377.1461; found: 377.1454.