3,6-Didehydro-5-hy­droxy-1,2-O-iso­propyl­idene-5-C-nitro­meth­yl-α-d-gluco­furan­ose

Qiurong Zhang; Pan Li; Xuebin Chen; Xiandong Wang; Hongmin Liu

doi:10.1107/S160053681102191X

. 2011 Jun 18;67(Pt 7):o1673. doi: 10.1107/S160053681102191X

3,6-Didehydro-5-hydroxy-1,2-O-isopropylidene-5-C-nitromethyl-α-d-glucofuranose

Qiurong Zhang ^a, Pan Li ^a, Xuebin Chen ^a, Xiandong Wang ^a, Hongmin Liu ^a,^*

PMCID: PMC3151982 PMID: 21837072

Abstract

The title compound, C₁₀H₁₅NO₇, consists of one methylenedioxy ring and two fused tetrahydrofuran rings. The three fused rings exhibit cis arrangements at the ring junctions. One O atom of a tetrahydrofuran ring and the H atoms bound to the neighboring C atoms are disordered over two orientations with site-occupancy factors of 0.69 (1) and 0.31 (1). intramolecular O—H⋯O and C—H⋯O interactions stabilize the molecular conformation. In the crystal structure, intermolecular O—H⋯O and C—H⋯O interactions link the molecules into a three-dimensional network.

Related literature

For the synthesis of azasugars, see: Choi et al. (1991 ▶); Kvaernø et al. (2001 ▶). For the Henry reaction used to obtain the title compound, see: Saito et al. (2002 ▶). For research on carbohydrates and azasugars, see: Liu et al. (2004 ▶); Ke et al. (2009 ▶); Zhang et al. (2011 ▶). For a similar structure, see: Zhang & Yang (2010 ▶).

Experimental

Crystal data

C₁₀H₁₅NO₇
M _r = 261.23
Orthorhombic,
a = 5.63290 (13) Å
b = 8.36405 (15) Å
c = 25.4014 (5) Å
V = 1196.76 (4) Å³
Z = 4
Cu Kα radiation
μ = 1.07 mm⁻¹
T = 291 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.783, T _max = 0.814
7427 measured reflections
2249 independent reflections
2161 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.165
S = 1.08
2249 reflections
174 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102191X/zq2104sup1.cif

e-67-o1673-sup1.cif^{(20KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102191X/zq2104Isup2.hkl

e-67-o1673-Isup2.hkl^{(110.6KB, 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
O5—H5⋯O4	0.86 (6)	2.13 (6)	2.696 (3)	123 (5)
O5—H5⋯O3ⁱ	0.86 (6)	2.24 (6)	2.703 (3)	114 (4)
C1—H1⋯O5ⁱⁱ	0.98	2.48	3.371 (3)	152
C4—H4⋯O6	0.98	2.39	3.074 (4)	126

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

Acknowledgments

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

supplementary crystallographic information

Comment

Azasugars containing some novel glycosyls such as bicyclo-glycosyl and heterocycle glycosyl, the synthesis of which being known for many years (Choi et al., 1991; Kvaernø et al., 2001), have attracted a growing interest due to their potent antiviral activity. As a contribution to the research for carbohydrate and azasugars compounds (Liu et al., 2004; Ke et al., 2009), we report here the synthesis and X-ray crystal structure of the title compound, an intermediate of bicyclo-glycosyl. The title compound, which shows a similar structure to the one previously reported by Zhang & Yang (2010), was enantiomerically synthesized at room tempeature by means of the Henry reaction (Saito et al., 2002).

The title compound, C₁₀H₁₅NO₇, consists of one methylenedioxy ring and two fused tetrahydrofuran rings. The three fused rings exhibit cis arrangements at the ring junctions and give two V-shaped molecules. One O atom of a tetrahydrofuran ring moiety is disordered over two positions with site-occupancy factors of 0.69 (1) and 0.31 (1), the H atoms bound to the neighboring C atoms were disordered as well. The bond angles O2—C7—O1 and C8—C7—C9 around the isopropylidene are 105.6 (2) and 113.2 (3)°, which are almost equal to the corresponding bond angles reported by Zhang & Yang (2010). The bond angle O5—C5—C10 containing simultaneously hydroxy and nitromethylene is 108.3 (2)°. The torsion angles C2—C3—C4—C5, O3—C3—C4—O4, O4—C1—C2—O2 and O1—C1—C2—C3 are -140.4 (3), 99.7 (4), 98.6 (3) and -135.2 (3) °, respectively.

In the crystal structure, some intra- and intermolecular O—H···O and C—H···O interactions exist to stabilize the molecular conformation and link the molecules into a three-dimensional network.

Experimental

The title compound was synthesized from 3,6-didehydro-1,2-O-isopropylidene-5-carbonyl-α-D-glucofuranose with Henry reaction as described previously by Saito et al. (2002) whose starting material was D-glucose. To a solution of the starting material (2.4 g, 9.2 mmol) in tetrahydrofuran (30 ml) was added CH₃NO₂ (0.82 ml) and potassium fluoride (0.84 g) under ice bath. The mixture was stirred at room temperature for 12 h. After the material was consumed, the reaction mixture was filtered to remove the KF. The filtrate was concentrated in vacuo to yield the residue, which was recrystalized in CH₃OH to obtain the title compound as a white solid. Crystals suitable for X-ray analysis were grown by slow evaporation from methanol at room temperature for two weeks.