Methyl 6-de­oxy-6-iodo-2,3-O-iso­propyl­idene-α-d-manno­pyran­oside

Zeynep Gültekin; Wolfgang Frey; Nagihan Çaylak Delibaş; Tuncer Hökelek

doi:10.1107/S1600536813022629

. 2013 Aug 17;69(Pt 9):o1449–o1450. doi: 10.1107/S1600536813022629

Methyl 6-deoxy-6-iodo-2,3-O-isopropylidene-α-d-mannopyranoside

Zeynep Gültekin ^a, Wolfgang Frey ^b, Nagihan Çaylak Delibaş ^c, Tuncer Hökelek ^d,^*

PMCID: PMC3884490 PMID: 24427076

Abstract

In the title compound, C₁₀H₁₇IO₅, the six-membered tetrahydropyran ring and the five-membered 1,3-dioxolane ring adopt sofa and envelope conformations, respectively. In the crystal, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into layers nearly parallel to the bc plane.

Related literature

For carbohydrates which are important for the preparation of unsaturated aldehydes, see: Kleban et al. (2000 ▶); Dransfield et al. (1999 ▶); Greul et al. (2001 ▶). For conversions of unsaturated aldehydes to oximes, nitrones and nitrile oxides, see: Dransfield et al. (1999 ▶); Bernet & Vasella (1979 ▶); Greul et al. (2001 ▶); Gallos et al. (1999 ▶); Kleban et al. (2001 ▶). For the methods reported in the literature for the preparation of the title compound, see: Garegg & Samuelsson (1980 ▶); Bundle et al. (1988 ▶); Ichikawa et al. (2004 ▶). For the synthesis of methyl 2,3-O-isopropylidene-α-d-mannopyranoside, see: Evans & Parrish (1977 ▶); Isobe et al. (1981 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₀H₁₇IO₅
M _r = 344.14
Monoclinic,
a = 8.3121 (8) Å
b = 10.3911 (10) Å
c = 8.3128 (8) Å
β = 118.639 (3)°
V = 630.15 (11) Å³
Z = 2
Mo Kα radiation
μ = 2.55 mm⁻¹
T = 100 K
0.99 × 0.58 × 0.44 mm

Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: numerical (Blessing, 1995 ▶) T _min = 0.187, T _max = 0.401
13656 measured reflections
3827 independent reflections
3803 reflections with I > 2σ(I)
R _int = 0.027
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.043
S = 1.24
3827 reflections
153 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.82 e Å⁻³
Absolute structure: Flack (1983 ▶), 1811 Friedel pairs
Absolute structure parameter: 0.003 (12)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813022629/xu5727sup1.cif

e-69-o1449-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813022629/xu5727Isup2.hkl

e-69-o1449-Isup2.hkl^{(183.8KB, 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—H2A⋯O3ⁱ	0.82 (3)	2.03 (3)	2.807 (2)	157 (3)
C10—H10C⋯O2ⁱⁱ	0.98	2.51	3.390 (3)	149

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

Acknowledgments

The authors are indebted to the Research Fund of Çankırı Karatekin University (grant No. BAP:2011/06) for financial support, and thank Professor V. Jäger of Stuttgart University, Germany, for helpful discussions.

supplementary crystallographic information

1. Comment

Various carbohydrates have been considerably important for the preparation of unsaturated aldehydes (Kleban et al., 2000; Dransfield et al., 1999; Greul et al., 2001). Conversions of unsaturated aldehydes to oximes (Dransfield et al., 1999), nitrones (Bernet & Vasella, 1979; Greul et al., 2001), nitrile oxides (Gallos et al., 1999; Kleban et al., 2001) and their intramolecular cycloadditions have been reported. These cycloadducts are useful intermediates for the syntheses of polyhydroxylated aminocyclopentane derivatives (Greul et al., 2001; Kleban et al., 2001).

In the title compound (Fig. 1), the ring A (C1–C5/O1) is not planar, but adopts a sofa conformation with puckering parameters (Cremer & Pople, 1975) Q_T = 0.551 (2) Å, φ = -113.1 (5)° and θ = 158.5 (2)°. The conformation of ring B (O4/O5/C3/C4/C8) is an envelope, with atom C4 at the flap position, -0.573 (2) Å from the mean plane through the other four atoms. Rings A and B have local pseudo-mirror planes running through C1 and C4 (for ring A), and running through C4 and the midpoint of the O4—C8 bond (for ring B).

In the crystal structure, intermolecular O—H···O and C—H···O hydrogen bonds (Table 1) link the molecules into layers nearly parallel to the bc plane (Fig. 2).

2. Experimental

The title compound was synthesized in two steps starting from α-D-mannopyranoside by the literature methods (Garegg & Samuelsson, 1980; Bundle et al., 1988; Ichikawa et al., 2004). To a solution of methyl 2,3-O-isopropylidene-α-D-mannopyranoside (Evans & Parrish, 1977; Isobe et al., 1981) (2.50 g, 10.66 mmol) in dry toluene (70 ml, dissolved at 353 K) were added PPh₃ (4.30 g, 15.90 mmol), imidazole (2.17 g, 31.98 mmol) and iodine (3.80 g, 14.90 mmol) sequentially. The reaction mixture was refluxed for 3 h. 20 ml water was added, and then the mixture was extracted with EtOAc (4 × 20 ml). The combined organic phase was washed with brine (300 ml) and then dried over MgSO₄. The filtrate was concentrated under reduced pressure, and the residue was purified by chromatography (PE:EE 70:30) to afford the iodo compound as a colourless crystalline solid (yield: 90%), m.p. 383–384 K.