2,3-O-Isopropyl­idene-3-C-phenyl­erythrofuran­ose

Tony V Robinson; Dennis K Taylor; Edward R T Tiekink

doi:10.1107/S160053680904848X

. 2009 Nov 21;65(Pt 12):o3129. doi: 10.1107/S160053680904848X

2,3-O-Isopropylidene-3-C-phenylerythrofuranose

Tony V Robinson ^a, Dennis K Taylor ^b,^‡, Edward R T Tiekink ^c,^*

PMCID: PMC2972136 PMID: 21578852

Abstract

The title compound, C₁₃H₁₆O, comprises two fused five-membered rings. Each ring has an envelope conformation, with the ether O atom in the furanose ring, and the CMe₂ atom in the acetonide ring as the flap atoms. In the crystal, centrosymmetrically related molecules associate via hydroxy–ether O—H⋯O hydrogen bonds and the resulting dimers are linked into a supramolecular chain with a flattened topology via C—H⋯O_hydroxy contacts, and aligned in the a-axis direction.

Related literature

For the relevance and chemistry of systems related to the title compound, see: Pedersen et al. (2009 ▶); Robinson et al. (2006 ▶, 2009 ▶); Valente et al. (2009 ▶). For the reactions of Co(II) complexes with endoperoxides, see: Boyd et al. (1980 ▶); Sutbeyaz et al. (1988 ▶); Greatrex et al. (2003 ▶); Greatrex & Taylor (2005 ▶). graphic file with name e-65-o3129-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₆O₄
M _r = 236.26
Triclinic,
a = 5.716 (2) Å
b = 9.201 (4) Å
c = 11.871 (6) Å
α = 89.76 (3)°
β = 78.72 (2)°
γ = 73.70 (2)°
V = 586.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.35 × 0.35 × 0.10 mm

Data collection

Rigaku AFC12κ/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.773, T _max = 1.000
14572 measured reflections
2408 independent reflections
2361 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.157
S = 1.16
2408 reflections
157 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904848X/sj2687sup1.cif

e-65-o3129-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904848X/sj2687Isup2.hkl

e-65-o3129-Isup2.hkl^{(115.9KB, 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—H2o⋯O1ⁱ	0.84	1.93	2.755 (2)	166
C5—H5a⋯O2ⁱⁱ	0.99	2.47	3.296 (3)	140

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

Acknowledgments

We are grateful to the Australian Research Council for financial support. TVR thanks the Commonwealth Government of Australia for a postgraduate scholarship.

supplementary crystallographic information

Comment

The dihydroxyation of monocyclic and bicyclic 1,2-dioxines has provided a new route for the stereoselective synthesis of a diverse range of carbohydrates and related compounds (Pedersen et al., 2009; Robinson et al., 2006; Robinson et al., 2009; Valente et al., 2009). During the course of these studies, the title compound, (I), was obtained by the Co(II)-mediated ring-opening of the precursor 1,2-dioxane, post dihydroxyation. The reactions of Co(II) complexes with endoperoxides have been well documented (Boyd et al., 1980; Sutbeyaz et al., 1988; Greatrex et al., 2003; Greatrex & Taylor, 2005).

The molecular structure of (I), Fig. 1, comprises two fused five-membered rings linked at the C3—C4 bond. Each of the five-membered rings adopts an envelope conformation, on atom O1 for the furanose (O1, C2—C5) ring, and on atom C6 for the acetonide (O3, O4, C3, C4, C6) ring. When viewed down the C3—C4 axis, the O1 atom lies above the plane through the four remaining atoms, away from the phenyl substituent and the C6 atom lies below the plane, being orientated in the same direction as the phenyl ring. In the crystal structure centrosymmetrically related pairs of molecules associate via O—H···O hydrogen bonds to form an eight-membered {···OCOH}₂ synthon, Table 1 and Fig. 2. The dimers are linked into a supramolecular chain via C—H···O contacts and ten-membered {···OH···OCH}₂ synthons, Table 1. The resulting chain comprising alternating eight- and ten-membered synthons has a flattened topology, Fig. 2, and is aligned along the a axis.

Experimental

For full synthetic procedures and characterization data see Pedersen et al. (2009) and Robinson et al. (2009). To a stirred solution of Co(salen)₂ (17 mg, 0.05 mmol) in THF (5 ml) at ambient temperature was added (3aR,7aS)-3a-phenyl-tetrahydro-2,2-dimethyl-[1,3]dioxolo[4,5-d][1,2]dioxine (501 mg, 2.12 mmol), and the reaction left to stir until complete by TLC (~16 h). All volatiles were removed in vacuo giving a crude mixture of regioisomers in a 40:60 ratio. The isomers were fully separated by flash chromatography giving a combined total yield of 496 mg (99%). Compound (I) was isolated as a colourless solid (198 mg), and the pure material was recrystallized from a slowly evaporating 1:1 mixture of dichloromethane/heptane to give colourless prisms, m. pt. 424–425 K. The compound was found to exist solely in its cyclic hemi-acetal form(s) both as a solid indicated by IR (absence of carbonyl signal), and in CDCl₃ solution which revealed a 90:10 ratio of anomers.