1,2;5,6-Di-O-isopropyl­idene-3-C-nitro­methyl-α-d-allofuran­ose

Qiurong Zhang; Yu Ke; Weiyan Cheng; Pengyun Li; Hongmin Liu

doi:10.1107/S1600536811017314

. 2011 May 14;67(Pt 6):o1402. doi: 10.1107/S1600536811017314

1,2;5,6-Di-O-isopropylidene-3-C-nitromethyl-α-d-allofuranose

Qiurong Zhang ^a, Yu Ke ^a, Weiyan Cheng ^a, Pengyun Li ^a, Hongmin Liu ^a,^*

PMCID: PMC3120445 PMID: 21754787

Abstract

The molecule of the title compound, C₁₃H₂₁NO₈, consists of two methylenedioxy rings and one tetrahydrofuran ring. In the crystal, intermolecular O—H⋯O hydrogen bonds link the molecules into helical chains running along the 6₁ screw axis. Weak intermolecular C—H⋯O hydrogen bonds help to stabilize the crystal packing. Voids of 245 Å³ per unit cell occur.

Related literature

For details of the synthesis, see: Saito et al. (2002 ▶). For recent studies of the biological activity of azasugars, see: Loiseleur et al. (2007 ▶); Rahman et al. (2008 ▶).

Experimental

Crystal data

C₁₃H₂₁NO₈
M _r = 319.31
Hexagonal,
a = 13.2581 (19) Å
c = 16.462 (3) Å
V = 2506.0 (7) Å³
Z = 6
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 291 K
0.24 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS-IV diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.975, T _max = 0.979
8380 measured reflections
1612 independent reflections
1534 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.164
S = 1.08
1612 reflections
205 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: R-AXIS-IV Software (Rigaku, 1997 ▶); cell refinement: R-AXIS-IV Software; data reduction: R-AXIS-IV Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: TEXSAN (Molecular Structure Corporation, 1992 ▶); software used to prepare material for publication: TEXSAN.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017314/cv5090sup1.cif

e-67-o1402-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017314/cv5090Isup2.hkl

e-67-o1402-Isup2.hkl^{(79.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3E⋯O6ⁱ	0.90 (8)	1.95 (8)	2.814 (5)	161 (7)
C1—H1A⋯O3ⁱⁱ	0.98	2.37	3.258 (4)	151
C5—H5A⋯O1ⁱⁱⁱ	0.98	2.50	3.320 (4)	141

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We gratefully acknowledge financial support by the National Natural Science Foundation of China (grant No. 20572103).

supplementary crystallographic information

Comment

Azasugars were recently used as novel glycosyls to synthesize novel N-nucleosides (Loiseleur et al., 2007; Rahman et al., 2008). Herewith we report the synthesis and crystal structure of the title compound (I) prepared in enantiomerically pure form from 1,2;5,6-di-O-isopropylidene-3-carbonyl-α-D-glucofuranose (Saito et al., 2002) at room tempeature, whose raw material was D-glucose.

The molecule of (I) consists of two methylenedioxy rings and one tetrahydrofuran ring (Fig. 1). In (I), the tetrahydrofuran ring fuses with one methylenedioxy ring, having the cis arrangement at the ring junctions and giving a V-shaped molecule. The angles O1—C8—O2, O5—C11—O6, C9—C8—C10 and C12—C11—C13 around the two isopropylidenes are 104.1 (4), 105.5 (4), 113.9 (5) and 114.2 (6)°, respectively.

In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 1) link the molecules into helical chains running along screw axis 6₁, and weak intermolecular C—H···O hydrogen bonds (Table 1) help to stabilize the crystal packing.

Experimental

All reagents and solvents were used as obtained without further purification. 1,2;5,6-di-O-isopropylidene-3-C-(nitromethyl)- α-D-allofuranose was synthesized from 1,2;5,6-di-O-isopropylidene-3-carbonyl-α-D-glucofuranose as described previously by Saito et al. (2002), whose starting material was D-glucose. To a solution of 1,2;5,6-di-O-isopropylidene-3-carbonyl -α-D-Glucofuranose (7.0 g, 27 mmol) in tetrahydrofuran (50 ml) was added CH₃NO₂ (10.5 ml) and potassium fluoride (3.0 g).The mixture was stirred at room temperature for 6 h. The reaction mixture was then concentrated in vacuo and extracted with water and EtOAc, dried (Na₂SO₄), and evaporated. The residue was recrystalied in CH₃OH to yield the title compound. Crystals suitable for X-ray analysis were grown by slow evaporation from methanol at room temperature for two weeks. R_f = 0.7 (CHCl₃/EtOAc, 7:3); mp: 110–111°C, [α]²⁰_D = +96° (c, 1.0, CH₃OH); ¹H NMR (400 MHz, CDCl₃) σ: 5.85(1H, d, J = 3.6 Hz), 4.97 (1H, d, J = 12 Hz), 4.89 (1H, d, J = 3.6 Hz), 4.49 (1H, d, J = 12 Hz), 4.13 (1H, m), 4.01(1H,m), 3.95 (1H, m), 3.89 (1H, d, J = 8.8), 3.27 (1H, s), 1.61 (3H, s), 1.47 (3H, s), 1.39 (3H, s), 1.36 (3H, s); ¹³C NMR (100 MHz, CDCl₃) σ: 113.3, 110.4, 103.7, 81.7, 79.8, 78.5, 77.6, 72.9, 67.9, 26.6, 26.5, 26.5, 25.0.