5-Azido-4-benz­yloxy-2-meth­oxy-6-methyl­perhydro­pyran-3-ol

Hoong-Kun Fun; Wan-Sin Loh; Sankappa Rai; Prakash Shetty; Arun M Isloor

doi:10.1107/S1600536809028657

. 2009 Jul 25;65(Pt 8):o1972. doi: 10.1107/S1600536809028657

5-Azido-4-benzyloxy-2-methoxy-6-methylperhydropyran-3-ol

Hoong-Kun Fun ^a,^*,^‡, Wan-Sin Loh ^a, Sankappa Rai ^b, Prakash Shetty ^c, Arun M Isloor ^d

PMCID: PMC2977377 PMID: 21583648

Abstract

In the title compound, C₁₄H₁₉N₃O₄, the perhydropyran ring adopts a chair conformation. An intramolecular C—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal packing, molecules are linked by O—H⋯O hydrogen bonds, forming infinite chains along [100].

Related literature

For background to d-perosamine, see: Jacquinet (2006 ▶). For the synthesis of d-perosamine, see: Krishna & Agrawal (2000 ▶). For metabolites, see: Grond et al. (2000 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₄H₁₉N₃O₄
M _r = 293.32
Orthorhombic,
a = 4.6662 (2) Å
b = 15.3356 (8) Å
c = 20.9273 (12) Å
V = 1497.54 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.27 × 0.11 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.773, T _max = 0.980
13029 measured reflections
1742 independent reflections
1334 reflections with I > 2σ(I)
R _int = 0.096

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.103
S = 1.09
1742 reflections
196 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028657/ng2616sup1.cif

e-65-o1972-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028657/ng2616Isup2.hkl

e-65-o1972-Isup2.hkl^{(85.8KB, 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
O2—H1O2⋯O2ⁱ	0.88 (4)	1.91 (3)	2.757 (2)	161 (3)
O2—H1O2⋯O3ⁱ	0.88 (3)	2.49 (3)	3.063 (3)	124 (3)
C7—H7B⋯O2	0.97	2.58	3.180 (4)	120

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Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). WSL thanks USM for a student assistantship.

supplementary crystallographic information

Comment

4-Amino-4,6-dideoxy-D-mannose (D-perosamine) was first discovered in the polyene macrolide antibiotic perimycin and was later recognized to be present in the lipopolysaccharide (LPS) of Vivrio cholera (Jacquinet, 2006). Methyl 3-benzyloxy-4-azido-α-D-rhamnopyranoside is an important intermediate in the synthesis of D-perosamine (Krishna & Agrawal, 2000). Rhamnopyranosides were detected as metabolites from five different strains of Streptomycetes (Grond et al., 2000).

The bond lengths (Allen et al., 1987) and angles in the molecule (Fig. 1) are within normal ranges. The perhydropyran ring adopts a chair conformation. The puckering parameters (Cremer & Pople, 1975) are Q = 0.540 (3) Å; Θ = 8.0 (3)° and φ = 8.0 (2)°. Intramolecular C7—H7B···O2 hydrogen bonds formed a six-membered ring, producing an S(6) ring motif (Bernstein et al., 1995). The dihedral angle formed between the benzene (C1—C6) and perhydropyran (C8—C10/O4/C11/C12) rings is 57.32 (16)°.

In the crystal packing (Fig. 2), the molecules are linked by intermolecular O2—H1O2···O2 and O2—H1O2···O3 hydrogen bonds (Table 1) into an infinite one-dimensional chains along the [100] direction.

Experimental

To a stirred mixture of methyl 3-benzyloxy-4-methoxysulfonyl-α-D-rhamnopyranoside (0.50 g, 1.4 mmol) in DMF (5.0 ml) was added sodium azide (0.18 g, 2.8 mmol). The reaction mixture was stirred further at room temperature for 12 h. TLC (30% EtOAc/hexane, Rf-0.5) analysis showed complete conversion. The reaction mixture was concentrated under vacuum and the residue was purified by column chromatography using 25% ethylacetate in petroleum ether to get pure product as colourless crystals (yield: 300.0 mg, 71%, M.p. 376–378 K).