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Acta Cryst. (2009). E65, o1456    [ doi:10.1107/S160053680902011X ]

(2S,4R,5S)-5-Allyl-4-hydroxytetrahydro-2-furylmethyl p-toluenesulfonate

E. Paz-Morales, F. Sartillo-Piscil and A. Mendoza

Abstract top

In the title compound, C15H20O5S, the tetrahydrofuran ring shows an envelope conformation. The crystal packing is stabilized by an intermolecular O-H...O hydrogen bond, generating a ribbon structure along the a axis. Two weak intermolecular C-H...O interactions are also observed.

Comment top

During the course of our investigations led to the synthesis of chiral tetrahydrofurans bearing an allyl group at C1 position (Romero et al., 2006; Sartillo-Melendez et al., 2006; Hernández-Garcia et al., 2009; Paz-Morales et al., 2009), the title compound was obtained and separated by crystallization from the its C1-epimer.

In the crystal structure, the tosyl ring and terminal double bond reach a close distance from each one (C7···C13 and C8···C12 = ca. 3.9 Å), with allyl π orbital being perpendicular for those of the aromatic ring. The furane ring (O1/C1–C4) shows an envelope conformation on atom C2 with puckering parameters (Cremer & Pople, 1975) q2 = 0.348 (8) Å and φ2 = 72.3 (12)°. The molecules are linked by hydrogen bond [O1···O5 = 2.782 (7) Å] interactions, building a ribbon structure along the [100] direction.

Related literature top

For the synthesis of chiral tetrahydrofurans bearing an allyl group at C1 positio, see: Romero et al. (2006); Sartillo-Melendez et al. (2006); Hernández-Garcia et al. (2009); Paz-Morales et al. (2009). For ring conformation analysis, see: Cremer & Pople (1975).

Experimental top

The title compound was obtained from a solution of 1,2-O-isopropylidene-α-D-xylofuranose derivative (1.0 mmol) in 10 ml of dry CH2Cl2. This was treated with allyltrimethylsilane (6.0 mmol) at room temperature over 10 min and the reaction mixture was cooled at 0 °C, then BF3OEt2 (6.0 mmol) was added dropwise. The reaction mixture was warmed at room temperature over 6 hrs and was treated with saturated aqueous solution of NaHCO3 (10 ml). The aqueous layer was extracted three times with CH2Cl2 (20 ml). The organic phase was dried with MgSO4, concentrated and purified by flash chromatography on silica gel (hexane: ethyl acetate). The absolute configuration was established by the structure determination of 1,2-O-isopropylidene-α-D-xylofuranose of known absolute configuration of starting material.

Refinement top

The H atom bonded to O atom was located in a difference map and the positional parameters were refined, with Uiso(H) = 1.5Ueq(O). C-bound H atoms were placed in geometrical idealized positions (C—H = 0.93–0.98 Å) and were refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS (Siemens, 1994); data reduction: XSCANS (Siemens, 1994); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of the title compound, showing molecules connected by O5—H···O1i hydrogen bonds and intermolecular weak interactions (dashed lines).
(2S,4R,5S)-5-Allyl-4-hydroxytetrahydro-2-furylmethyl p-toluenesulfonate top
Crystal data top
C15H20O5SF(000) = 332
Mr = 312.37Dx = 1.275 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 40 reflections
a = 5.9420 (12) Åθ = 4.8–24.7°
b = 16.966 (3) ŵ = 0.22 mm−1
c = 8.1980 (19) ÅT = 293 K
β = 100.09 (2)°Prism, colorless
V = 813.7 (3) Å30.6 × 0.4 × 0.3 mm
Z = 2
Data collection top
Bruker P4
diffractometer		Rint = 0.030
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 2.4°
graphiteh = −1→7
2θ/ω scansk = −1→20
2127 measured reflectionsl = −9→9
1575 independent reflections3 standard reflections every 97 reflections
1099 reflections with I > 2σ(I) intensity decay: 7%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126 w = 1/[σ2(Fo2) + (0.0261P)2 + 0.5527P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1575 reflectionsΔρmax = 0.26 e Å−3
194 parametersΔρmin = −0.23 e Å−3
1 restraintAbsolute structure: Flack (1983), 97 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.1 (2)
Crystal data top
C15H20O5SV = 813.7 (3) Å3
Mr = 312.37Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.9420 (12) ŵ = 0.22 mm−1
b = 16.966 (3) ÅT = 293 K
c = 8.1980 (19) Å0.6 × 0.4 × 0.3 mm
β = 100.09 (2)°
Data collection top
Bruker P4
diffractometer		Rint = 0.030
2127 measured reflectionsθmax = 25.5°
1575 independent reflections3 standard reflections every 97 reflections
1099 reflections with I > 2σ(I) intensity decay: 7%
Refinement top
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126Δρmax = 0.26 e Å−3
S = 1.07Δρmin = −0.23 e Å−3
1575 reflectionsAbsolute structure: Flack (1983), 97 Friedel pairs
194 parametersFlack parameter: −0.1 (2)
1 restraint
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.2153 (3)0.44181 (11)0.35980 (19)0.0535 (4)
O4−0.0229 (6)0.4463 (4)0.3656 (5)0.0664 (12)
O20.2892 (7)0.5318 (3)0.3599 (6)0.0586 (12)
C90.3645 (10)0.4054 (4)0.5478 (7)0.0456 (14)
O10.5274 (7)0.6525 (3)0.5384 (7)0.0707 (15)
O30.2936 (8)0.4018 (3)0.2256 (5)0.0673 (14)
O51.1076 (9)0.7133 (4)0.5830 (9)0.092 (2)
C100.5693 (10)0.3653 (4)0.5528 (8)0.0488 (15)
H100.62870.35750.45640.059*
C40.5632 (11)0.6353 (4)0.3722 (9)0.0615 (19)
H40.45580.66600.29260.074*
C110.6847 (12)0.3367 (4)0.7038 (9)0.0611 (19)
H110.82220.31000.70770.073*
C140.2741 (12)0.4168 (4)0.6894 (8)0.0614 (19)
H140.13770.44410.68600.074*
C20.9228 (11)0.6608 (4)0.5423 (10)0.065 (2)
H20.97190.60730.57700.077*
C50.5240 (11)0.5496 (4)0.3390 (9)0.0626 (19)
H5A0.54460.53700.22710.075*
H5B0.63170.51860.41580.075*
C30.8076 (12)0.6601 (5)0.3629 (10)0.075 (2)
H3A0.87990.62250.29940.090*
H3B0.81100.71190.31350.090*
C130.3905 (13)0.3868 (5)0.8364 (9)0.070 (2)
H130.32740.39310.93170.084*
C120.5976 (12)0.3476 (5)0.8486 (8)0.065 (2)
C10.7298 (11)0.6868 (5)0.6323 (10)0.068 (2)
H10.71590.74420.62440.082*
C150.7242 (14)0.3163 (6)1.0118 (9)0.092 (3)
H15A0.74230.26031.00400.138*
H15B0.63880.32801.09800.138*
H15C0.87190.34081.03700.138*
C70.765 (2)0.5786 (7)0.8486 (12)0.100 (3)
H70.64370.54660.80070.120*
C60.7504 (16)0.6637 (5)0.8113 (11)0.088 (3)
H6A0.88570.68880.87280.106*
H6B0.61960.68490.85260.106*
C80.938 (2)0.5455 (8)0.9454 (12)0.135 (5)
H8A1.06090.57600.99490.162*
H8B0.93750.49150.96450.162*
H5O1.26 (2)0.695 (7)0.578 (14)0.162*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0460 (8)0.0574 (9)0.0559 (9)−0.0012 (9)0.0053 (7)0.0015 (10)
O40.038 (2)0.080 (3)0.081 (3)−0.001 (3)0.010 (2)0.008 (4)
O20.044 (2)0.050 (3)0.084 (3)−0.003 (2)0.017 (2)0.008 (2)
C90.046 (3)0.043 (3)0.048 (3)−0.006 (3)0.008 (3)0.002 (3)
O10.035 (2)0.087 (4)0.093 (4)−0.009 (3)0.020 (2)−0.010 (3)
O30.078 (3)0.079 (3)0.046 (2)−0.003 (3)0.013 (2)−0.015 (2)
O50.050 (3)0.082 (4)0.146 (5)−0.010 (3)0.022 (4)−0.015 (4)
C100.042 (4)0.052 (4)0.054 (4)−0.004 (3)0.013 (3)−0.005 (3)
C40.049 (4)0.052 (4)0.082 (5)0.005 (3)0.009 (4)0.016 (4)
C110.053 (4)0.059 (5)0.068 (4)0.008 (4)0.000 (3)0.009 (4)
C140.062 (4)0.073 (5)0.051 (4)0.010 (4)0.013 (3)−0.006 (3)
C20.033 (3)0.051 (4)0.109 (6)−0.001 (3)0.012 (4)0.001 (4)
C50.048 (4)0.061 (4)0.083 (5)0.004 (4)0.021 (4)0.012 (4)
C30.056 (4)0.072 (5)0.102 (6)−0.012 (4)0.028 (4)0.018 (5)
C130.068 (5)0.089 (6)0.055 (4)0.007 (4)0.017 (4)−0.007 (4)
C120.062 (5)0.072 (5)0.057 (4)−0.013 (4)0.000 (3)−0.001 (4)
C10.041 (4)0.061 (5)0.104 (6)0.007 (3)0.017 (4)0.003 (4)
C150.091 (6)0.109 (7)0.066 (5)−0.001 (6)−0.010 (4)0.028 (5)
C70.117 (9)0.100 (8)0.080 (6)−0.020 (7)0.014 (6)−0.011 (6)
C60.076 (6)0.083 (7)0.108 (7)−0.011 (5)0.022 (5)−0.017 (6)
C80.181 (12)0.135 (10)0.088 (7)0.042 (10)0.023 (8)0.016 (7)
Geometric parameters (Å, °) top
S1—O41.427 (4)C2—C11.533 (9)
S1—O31.437 (5)C2—H20.9800
S1—O21.589 (5)C5—H5A0.9700
S1—C91.751 (6)C5—H5B0.9700
O2—C51.467 (7)C3—H3A0.9700
C9—C141.375 (8)C3—H3B0.9700
C9—C101.389 (8)C13—C121.386 (10)
O1—C11.433 (8)C13—H130.9300
O1—C41.445 (8)C12—C151.512 (9)
O5—C21.408 (8)C1—C61.503 (11)
O5—H5O0.96 (11)C1—H10.9800
C10—C111.392 (9)C15—H15A0.9600
C10—H100.9300C15—H15B0.9600
C4—C51.490 (10)C15—H15C0.9600
C4—C31.526 (9)C7—C81.311 (14)
C4—H40.9800C7—C61.475 (13)
C11—C121.388 (9)C7—H70.9300
C11—H110.9300C6—H6A0.9700
C14—C131.378 (9)C6—H6B0.9700
C14—H140.9300C8—H8A0.9300
C2—C31.509 (10)C8—H8B0.9300
O4—S1—O3120.5 (3)H5A—C5—H5B108.5
O4—S1—O2103.0 (3)C2—C3—C4103.1 (6)
O3—S1—O2109.1 (3)C2—C3—H3A111.1
O4—S1—C9110.0 (3)C4—C3—H3A111.1
O3—S1—C9109.0 (3)C2—C3—H3B111.1
O2—S1—C9104.0 (3)C4—C3—H3B111.1
C5—O2—S1117.7 (4)H3A—C3—H3B109.1
C14—C9—C10120.9 (6)C14—C13—C12122.9 (7)
C14—C9—S1118.7 (5)C14—C13—H13118.6
C10—C9—S1120.3 (5)C12—C13—H13118.6
C1—O1—C4109.9 (5)C13—C12—C11117.5 (6)
C2—O5—H5O119 (7)C13—C12—C15122.0 (7)
C9—C10—C11119.3 (6)C11—C12—C15120.5 (7)
C9—C10—H10120.4O1—C1—C6109.6 (6)
C11—C10—H10120.4O1—C1—C2104.6 (6)
O1—C4—C5109.0 (6)C6—C1—C2117.1 (7)
O1—C4—C3106.9 (6)O1—C1—H1108.4
C5—C4—C3112.3 (6)C6—C1—H1108.4
O1—C4—H4109.6C2—C1—H1108.4
C5—C4—H4109.6C12—C15—H15A109.5
C3—C4—H4109.6C12—C15—H15B109.5
C12—C11—C10121.0 (7)H15A—C15—H15B109.5
C12—C11—H11119.5C12—C15—H15C109.5
C10—C11—H11119.5H15A—C15—H15C109.5
C9—C14—C13118.4 (6)H15B—C15—H15C109.5
C9—C14—H14120.8C8—C7—C6123.7 (12)
C13—C14—H14120.8C8—C7—H7118.1
O5—C2—C3116.0 (7)C6—C7—H7118.1
O5—C2—C1108.8 (6)C7—C6—C1116.7 (8)
C3—C2—C1102.8 (6)C7—C6—H6A108.1
O5—C2—H2109.7C1—C6—H6A108.1
C3—C2—H2109.7C7—C6—H6B108.1
C1—C2—H2109.7C1—C6—H6B108.1
O2—C5—C4107.5 (5)H6A—C6—H6B107.3
O2—C5—H5A110.2C7—C8—H8A120.0
C4—C5—H5A110.2C7—C8—H8B120.0
O2—C5—H5B110.2H8A—C8—H8B120.0
C4—C5—H5B110.2
O4—S1—O2—C5−174.5 (5)O5—C2—C3—C4−151.9 (6)
O3—S1—O2—C5−45.4 (5)C1—C2—C3—C4−33.3 (8)
C9—S1—O2—C570.8 (5)O1—C4—C3—C221.1 (8)
O4—S1—C9—C14−26.7 (6)C5—C4—C3—C2−98.3 (8)
O3—S1—C9—C14−160.7 (5)C9—C14—C13—C121.9 (12)
O2—S1—C9—C1483.0 (6)C14—C13—C12—C11−2.0 (12)
O4—S1—C9—C10152.9 (5)C14—C13—C12—C15179.0 (8)
O3—S1—C9—C1018.9 (6)C10—C11—C12—C130.9 (11)
O2—S1—C9—C10−97.4 (5)C10—C11—C12—C15179.9 (7)
C14—C9—C10—C11−0.4 (9)C4—O1—C1—C6−148.3 (6)
S1—C9—C10—C11−179.9 (5)C4—O1—C1—C2−21.9 (8)
C1—O1—C4—C5122.2 (6)O5—C2—C1—O1158.0 (6)
C1—O1—C4—C30.6 (8)C3—C2—C1—O134.5 (8)
C9—C10—C11—C120.2 (10)O5—C2—C1—C6−80.5 (9)
C10—C9—C14—C13−0.6 (10)C3—C2—C1—C6156.1 (7)
S1—C9—C14—C13178.9 (6)C8—C7—C6—C1120.2 (11)
S1—O2—C5—C4−170.4 (5)O1—C1—C6—C759.6 (11)
O1—C4—C5—O258.8 (7)C2—C1—C6—C7−59.3 (12)
C3—C4—C5—O2177.0 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5O···O1i0.96 (11)1.83 (11)2.782 (7)171 (10)
C5—H5B···O4i0.972.493.188 (8)129
C13—H13···O3ii0.932.463.350 (8)161
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5O···O1i0.96 (11)1.83 (11)2.782 (7)171 (10)
C5—H5B···O4i0.972.493.188 (8)129
C13—H13···O3ii0.932.463.350 (8)161
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1.
Acknowledgements top

We gratefully acknowledge financial support from CONACYT (grant No. 62203 and Graduate Scholarship 159362) and Facultad de Ciencias Químicas (BUAP).

references
References top

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