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Acta Cryst. (2007). E63, o3387    [ doi:10.1107/S1600536807031510 ]

2,3-C-Dimethyl-3,4-O-isopropylidene-D-allono-1,5-lactone

L. A. Curran, S. F. Jenkinson, N. A. Jones, D. J. Watkin and G. W. J. Fleet

Abstract top

The relative configuration of the title compound, C11H18O6, was firmly established by X-ray crystallographic analysis. The absolute configuration was determined by the use of 2-C-methyl-D-ribono-1,4-lactone as the starting material. The structure exists as a hydrogen-bonded network, with each molecule acting as a donor and acceptor for two hydrogen bonds.

Comment top

Branched sugars are a relatively unstudied class of compounds but recent biological results have indicated they could have a potential use as therapeutics (Mitchell et al. 2007). The Kiliani ascension on ketoses and deoxy ketoses has proved a valuable route towards branched sugars (Hotchkiss et al., 2004,2006; Soengas et al., 2005; Jones, Watkin et al. 2007). Currently, there are very limited examples of di-branched carbohydrates reported. Examples of sugars that contain two carbon branches in the literature include 2,4-C-dimethyl-3,4-O-isopropylidene-L-arabinono-1,5-lactone (Booth, Watkin et al. 2007) and various protected forms of 3,5-C-dimethyl-mannono and glucono lactone (Booth, Jenkinson, Fleet & Watkin, 2007a, 2007b, 2007c). 2-C-Hydroxymethyl-2,3-O-isopropylidene-3-C-methyl-β-L– erythrose (Booth, Jenkinson, Watkin & Fleet, 2007d) is a rare example of a sugar with adjacent branched centres.

The crystal structure of the title compound (Fig. 1) exists as a three dimensionally hydrogen bonded network (Fig. 2) with each molecule acting as an acceptor and a donor for two hydrogen bonds.

Related literature top

For related literature see: Jones, Curran et al. (2007); Jones, Watkin et al. (2007); Mitchell et al. (2007); Hotchkiss et al. (2004, 2006); Soengas et al. (2005); Booth, Watkin et al. (2007); Booth et al. (2007a, 2007b, 2007c, 2007d); Curran et al. (2007); Görbitz (1999).

Experimental top

Treatment of 1-deoxy-3-C-methyl-D-psicose 2 (Jones et al. in preparation) derived from 2-C-methyl-D-ribono-1,4-lactone 1 (Hotchkiss et al., 2006), with sodium cyanide, gave a mixture of the 2,6-anhydro derivative 3 (Curran et al. 2007) and the lactone 4 (Fig. 3). X-Ray crystallographic analysis of the title lactone 3 removed any ambiguity as to the stereochemistry at the new C-2 chiral centre. The title compound was recrystallized from a mixture of cyclohexane and ethyl acetate; m.p. 420 K; [α]D22 +106.1 (c, 0.64 in chlororform).

Refinement top

In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned from the starting material.

The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:1.19) reflect changes in the illuminated volume of the crystal. Changes in illuminated volume were kept to a minimum, and were taken into account (Görbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997).

The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, O—H = 0.82 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.

Computing details top

Data collection: COLLECT (Nonius, 2001).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
[Figure 2] Fig. 2. The packing of the title compound projected along the a-axis. Hydrogen bonds are shown as dotted lines.
[Figure 3] Fig. 3. The reaction scheme.
2,3-C-Dimethyl-3,4-O-isopropylidene-D-allono-1,5-lactone top
Crystal data top
C11H18O6F(000) = 528
Mr = 246.26Dx = 1.361 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1357 reflections
a = 6.9089 (2) Åθ = 5–27°
b = 12.2072 (5) ŵ = 0.11 mm−1
c = 14.2507 (5) ÅT = 150 K
V = 1201.88 (7) Å3Plate, colourless
Z = 40.20 × 0.20 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer		1303 reflections with I > 2.0σ(I)
graphiteRint = 0.031
ω scansθmax = 27.5°, θmin = 5.2°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)		h = −8→8
Tmin = 0.83, Tmax = 0.99k = −15→15
5554 measured reflectionsl = −18→18
1561 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.073 w = 1/[σ2(F2) + (0.03P)2 + 0.22P],
where P = [max(Fo2,0) + 2Fc2]/3
S = 0.92(Δ/σ)max = 0.0002
1561 reflectionsΔρmax = 0.26 e Å−3
154 parametersΔρmin = −0.24 e Å−3
0 restraints
Crystal data top
C11H18O6V = 1201.88 (7) Å3
Mr = 246.26Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.9089 (2) ŵ = 0.11 mm−1
b = 12.2072 (5) ÅT = 150 K
c = 14.2507 (5) Å0.20 × 0.20 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer		1561 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)		1303 reflections with I > 2.0σ(I)
Tmin = 0.83, Tmax = 0.99Rint = 0.031
5554 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.073Δρmax = 0.26 e Å−3
S = 0.92Δρmin = −0.24 e Å−3
1561 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6355 (3)0.35060 (15)0.21409 (12)0.0168
C20.7020 (3)0.45680 (13)0.26378 (12)0.0185
C30.7261 (3)0.42656 (14)0.36718 (13)0.0225
O40.5794 (2)0.37424 (10)0.40921 (8)0.0233
C50.4030 (3)0.34688 (15)0.35788 (12)0.0191
C60.4458 (3)0.30862 (13)0.25760 (12)0.0173
O70.29790 (19)0.34924 (10)0.19778 (8)0.0190
C80.3790 (3)0.35046 (16)0.10563 (12)0.0194
O90.57947 (19)0.38010 (10)0.12033 (8)0.0198
C100.2817 (3)0.43932 (15)0.04956 (13)0.0249
C110.3659 (3)0.23797 (15)0.06080 (13)0.0262
C120.3044 (3)0.25957 (14)0.41507 (13)0.0234
O130.4187 (2)0.16239 (10)0.41357 (8)0.0249
O140.8717 (2)0.44346 (11)0.41227 (9)0.0336
O150.54750 (19)0.53432 (9)0.26178 (9)0.0216
C160.8859 (3)0.50609 (16)0.22511 (14)0.0263
C170.7921 (3)0.26278 (15)0.21373 (13)0.0238
H510.32150.41240.35520.0251*
H610.44700.22630.25670.0225*
H1010.34380.4423−0.01180.0346*
H1020.29850.50930.08390.0349*
H1030.14550.41930.04240.0349*
H1110.41830.2437−0.00330.0397*
H1120.44150.18520.09880.0394*
H1130.23180.21410.05790.0391*
H1210.28800.28710.48020.0300*
H1220.17410.24320.38860.0301*
H1610.90860.57570.25810.0405*
H1620.99370.45540.23530.0400*
H1630.86970.51980.15810.0397*
H1710.74280.19790.18040.0363*
H1720.90470.29370.18240.0372*
H1730.82350.24340.27920.0366*
H50.54310.56040.20650.0319*
H190.39900.11940.45860.0389*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0184 (9)0.0180 (9)0.0140 (8)0.0009 (8)−0.0006 (8)0.0008 (7)
C20.0215 (10)0.0159 (7)0.0181 (8)0.0009 (8)−0.0027 (8)0.0033 (8)
C30.0301 (12)0.0158 (8)0.0216 (9)−0.0012 (9)−0.0041 (9)−0.0001 (8)
O40.0286 (8)0.0239 (7)0.0173 (6)−0.0042 (7)−0.0033 (6)0.0011 (6)
C50.0204 (10)0.0199 (9)0.0169 (8)0.0024 (9)0.0000 (8)0.0005 (8)
C60.0181 (9)0.0165 (8)0.0172 (8)0.0006 (8)0.0003 (9)0.0003 (8)
O70.0157 (7)0.0246 (7)0.0166 (6)0.0007 (6)−0.0010 (6)0.0013 (6)
C80.0157 (10)0.0267 (10)0.0158 (8)−0.0028 (9)0.0016 (8)0.0012 (8)
O90.0172 (7)0.0270 (7)0.0153 (6)−0.0030 (6)−0.0005 (6)0.0012 (5)
C100.0229 (11)0.0283 (10)0.0234 (9)−0.0010 (10)−0.0045 (9)0.0060 (9)
C110.0289 (11)0.0287 (10)0.0210 (9)−0.0025 (10)−0.0037 (9)−0.0021 (9)
C120.0267 (11)0.0234 (9)0.0202 (9)0.0010 (10)0.0057 (9)0.0011 (8)
O130.0355 (8)0.0184 (6)0.0208 (6)0.0030 (7)0.0048 (6)0.0049 (5)
O140.0384 (9)0.0354 (8)0.0272 (7)−0.0107 (8)−0.0143 (7)0.0073 (7)
O150.0279 (8)0.0153 (5)0.0217 (6)0.0026 (6)−0.0007 (7)0.0029 (6)
C160.0242 (11)0.0258 (10)0.0288 (10)−0.0055 (9)−0.0040 (10)0.0066 (9)
C170.0223 (10)0.0223 (9)0.0268 (10)0.0049 (9)−0.0008 (9)−0.0014 (8)
Geometric parameters (Å, °) top
C1—C21.547 (2)C8—C111.517 (3)
C1—C61.538 (2)C10—H1010.975
C1—O91.437 (2)C10—H1020.991
C1—C171.524 (2)C10—H1030.977
C2—C31.528 (2)C11—H1110.985
C2—O151.427 (2)C11—H1120.990
C2—C161.510 (3)C11—H1130.972
C3—O41.339 (2)C12—O131.425 (2)
C3—O141.212 (2)C12—H1210.994
O4—C51.460 (2)C12—H1220.996
C5—C61.532 (2)O13—H190.840
C5—C121.505 (3)O15—H50.850
C5—H510.979C16—H1610.983
C6—O71.420 (2)C16—H1620.979
C6—H611.005C16—H1630.976
O7—C81.428 (2)C17—H1710.984
C8—O91.447 (2)C17—H1720.972
C8—C101.506 (3)C17—H1730.987
C2—C1—C6110.36 (15)C10—C8—C11113.71 (15)
C2—C1—O9107.19 (13)C8—O9—C1109.25 (14)
C6—C1—O9103.24 (13)C8—C10—H101107.8
C2—C1—C17112.35 (15)C8—C10—H102107.8
C6—C1—C17111.86 (14)H101—C10—H102111.0
O9—C1—C17111.37 (14)C8—C10—H103107.8
C1—C2—C3105.74 (13)H101—C10—H103109.8
C1—C2—O15108.93 (14)H102—C10—H103112.3
C3—C2—O15105.12 (15)C8—C11—H111107.8
C1—C2—C16114.64 (16)C8—C11—H112109.1
C3—C2—C16110.89 (16)H111—C11—H112111.1
O15—C2—C16110.97 (13)C8—C11—H113110.2
C2—C3—O4117.66 (17)H111—C11—H113109.3
C2—C3—O14124.09 (18)H112—C11—H113109.3
O4—C3—O14118.19 (16)C5—C12—O13109.30 (15)
C3—O4—C5121.10 (13)C5—C12—H121108.6
O4—C5—C6112.08 (15)O13—C12—H121111.0
O4—C5—C12105.58 (14)C5—C12—H122110.2
C6—C5—C12112.12 (15)O13—C12—H122109.2
O4—C5—H51108.2H121—C12—H122108.6
C6—C5—H51108.9C12—O13—H19114.7
C12—C5—H51109.9C2—O15—H5107.0
C1—C6—C5116.03 (15)C2—C16—H161107.7
C1—C6—O7104.76 (12)C2—C16—H162109.5
C5—C6—O7108.34 (14)H161—C16—H162110.7
C1—C6—H61108.7C2—C16—H163109.2
C5—C6—H61108.5H161—C16—H163109.8
O7—C6—H61110.4H162—C16—H163109.9
C6—O7—C8105.87 (13)C1—C17—H171108.8
O7—C8—O9104.19 (13)C1—C17—H172107.3
O7—C8—C10108.69 (15)H171—C17—H172111.6
O9—C8—C10108.91 (15)C1—C17—H173108.7
O7—C8—C11110.77 (15)H171—C17—H173109.9
O9—C8—C11110.13 (16)H172—C17—H173110.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O15—H5···O13i0.852.132.957 (2)163
O13—H19···O14ii0.842.002.817 (2)163
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O15—H5···O13i0.852.132.957 (2)163
O13—H19···O14ii0.842.002.817 (2)163
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1.
Acknowledgements top

Any acknowledgements?

references
References top

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