organic compounds
3-Deoxy-D-galactono-1,4-lactone (3-deoxy-D-xylo-hexono-1,4-lactone)
aDipartimento di Scienze Chimiche, Facoltà di Farmacia, Università di Catania, Viale A. Doria 6, 95125 Catania, Italy, bDepartment of Chemical Crystallography, Chemical Research Laboratory, Mansfield Road, Oxford OX1 3TA, England, and cDepartment of Organic Chemistry, Chemical Research Laboratory, Mansfield Road, Oxford OX1 3TA, England
*Correspondence e-mail: fpunzo@unict.it
On the basis of the known D-galactose, the structural study of 3-deoxy-D-xylo-galactono-1,4-lactone, C6H10O5 a valuable synthetic intermediate, allowed the unambiguous confirmation that the chiral centre at position 2 has the R configuration. This centre is formed during synthesis of the title compound from D-galactose under environmentally friendly conditions. Three symmetry-independent intermolecular hydrogen bonds link the molecules into layers parallel to the ac plane.
ofComment
A number of useful synthetic carbohydrate scaffolds, including several branched carbohydrate ) can be obtained by the treatment of hexoses with aqueous calcium hydroxide (Bols, 1996). In recent times, the deoxy lactone (1), also known as α-D-galactometasaccharinic acid, has usually been obtained by a three-step synthesis from D-galactonolactone involving organic solvents and reagents (Bock et al., 1981, 1986; Choquet-Farnier et al., 1997). However, a green aqueous procedure allows preparation of lactone (1) directly by treatment of galactose (2) with aqueous calcium hydroxide (Whistler & BeMiller, 1963; Kiliani & Kleeman, 1884). This is the prefered route, not only because of the environmentally friendly conditions, but also due to the low cost of galactose (2), the starting material, whose price represents just a small fraction of the cost of D-galactonolactone. It is noteworthy that completely different products arise if sugar (2) is treated with a secondary amine such as dibenzylamine prior to the reaction with calcium hydroxide; in that case the major isolated product is the branched lyxono-1,4-lactone (3) (Punzo et al., 2006).
(Monneret & Florent, 1994Lactone (1) can be readily obtained and has a great potential as a chiral building block for the synthesis of complex highly functionalized targets. It has already been used for the synthesis of carnitine (Bols et al., 1992) and hydroxylated azepanes (Anderson et al., 2000); it can also prove useful for synthesis of bulgecinines and other highly substituted prolines and pyrrolidines.
This paper reports the ). The use of D-galactose as starting material defines the of the two stereogenic centres at C4 and C5; the present structural study establishes unambiguously that the chiral centre at C2 has the R configuration.
of (1), prepared from galactose and calcium hydroxide, and unambiguously establishes the relative stereochemistry (Fig. 1The packing of (1) is shown in Fig. 2. Each of the three symmetry-independent `active' H atoms in the molecule of (1) is involved in hydrogen bonding (Table 2). Atoms H11 and H9 form the hydrogen bonds which link molecules into double chains along the c axis. These chains are further aggregated into layers parallel to the ac plane via hydrogen bonds involving H10.
Experimental
The title compound [m.p. 414–415 K, [α]21D −43.8 (c 1.24 in water)] was synthesized according to Sowden et al. (1957) [literature m.p. 415–416 K, [α]25D −47.8 (c 1 in water); Sowden, 1957; Sowden et al., 1957)]. It was then dissolved in methanol in a small sealed glass flask and left for 24 h in an oven at 313 K and for a further night at room temperature. Thereafter, the flask was opened to let the solvent slowly evaporate and colourless prismatic crystals were formed. A suitable piece was cut from a larger crystal.
Crystal data
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Refinement
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H atoms were located in a difference map, but those attached to C 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 = 0.93–98 Å and O—H = 0.82 Å) and isotropic displacement parameters [Uiso(H) = 1.2–1.5Ueq(C,O)], after which their positions were refined with riding constraints. In the absence of significant Friedel pairs were merged.
Data collection: COLLECT (Nonius, 2001).; cell 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.
Supporting information
https://doi.org/10.1107/S1600536806008099/ya6281sup1.cif
contains datablocks global, 1. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S1600536806008099/ya62811sup2.hkl
Data collection: COLLECT (Nonius, 2001).; cell
DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); 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.C6H10O5 | Dx = 1.514 Mg m−3 |
Mr = 162.14 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 787 reflections |
a = 5.3320 (2) Å | θ = 5.1–27.5° |
b = 8.4865 (3) Å | µ = 0.13 mm−1 |
c = 15.7238 (8) Å | T = 100 K |
V = 711.50 (5) Å3 | Prism, colourless |
Z = 4 | 0.60 × 0.50 × 0.40 mm |
F(000) = 344 |
Nonius Kappa CCD diffractometer | 896 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.010 |
ω scans | θmax = 27.4°, θmin = 5.2° |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −6→6 |
Tmin = 0.935, Tmax = 0.948 | k = −10→10 |
1521 measured reflections | l = −20→20 |
942 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(F2) + (0.01P)2 + 0.2P] where P = [max(Fo2,0) + 2Fc2]/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
942 reflections | Δρmax = 0.18 e Å−3 |
100 parameters | Δρmin = −0.20 e Å−3 |
0 restraints |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2537 (3) | 0.48508 (18) | 0.13488 (8) | 0.0128 | |
C5 | 0.1466 (3) | 0.38063 (17) | 0.20404 (9) | 0.0132 | |
C6 | 0.3508 (3) | 0.28675 (17) | 0.24829 (9) | 0.0150 | |
O11 | 0.5368 (2) | 0.38909 (12) | 0.28445 (6) | 0.0161 | |
O10 | 0.0167 (2) | 0.47603 (12) | 0.26456 (6) | 0.0152 | |
O7 | 0.0425 (2) | 0.56286 (12) | 0.09076 (6) | 0.0147 | |
C2 | 0.0865 (3) | 0.56805 (16) | 0.00679 (9) | 0.0136 | |
C3 | 0.3376 (3) | 0.49259 (17) | −0.01439 (8) | 0.0141 | |
C4 | 0.3926 (3) | 0.39601 (19) | 0.06479 (9) | 0.0170 | |
O9 | 0.3231 (2) | 0.39745 (12) | −0.08780 (6) | 0.0183 | |
O8 | −0.0638 (2) | 0.62617 (12) | −0.04183 (6) | 0.0187 | |
H1 | 0.3564 | 0.5673 | 0.1606 | 0.0150* | |
H5 | 0.0291 | 0.3090 | 0.1773 | 0.0154* | |
H61 | 0.4367 | 0.2198 | 0.2072 | 0.0185* | |
H62 | 0.2698 | 0.2217 | 0.2943 | 0.0191* | |
H3 | 0.4581 | 0.5767 | −0.0206 | 0.0171* | |
H41 | 0.3208 | 0.2890 | 0.0583 | 0.0204* | |
H42 | 0.5707 | 0.3891 | 0.0770 | 0.0200* | |
H10 | −0.1376 | 0.4487 | 0.2687 | 0.0258* | |
H11 | 0.5184 | 0.3894 | 0.3385 | 0.0266* | |
H9 | 0.3699 | 0.4526 | −0.1325 | 0.0289* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0112 (7) | 0.0146 (7) | 0.0127 (6) | 0.0008 (6) | −0.0023 (6) | −0.0006 (6) |
C5 | 0.0132 (7) | 0.0141 (7) | 0.0122 (6) | −0.0022 (6) | 0.0003 (6) | −0.0028 (5) |
C6 | 0.0149 (7) | 0.0136 (7) | 0.0166 (6) | −0.0004 (6) | −0.0015 (7) | 0.0001 (6) |
O11 | 0.0123 (5) | 0.0238 (5) | 0.0122 (4) | −0.0021 (5) | −0.0010 (4) | 0.0002 (4) |
O10 | 0.0116 (5) | 0.0206 (5) | 0.0132 (5) | −0.0001 (4) | 0.0015 (4) | −0.0038 (4) |
O7 | 0.0145 (5) | 0.0189 (5) | 0.0107 (4) | 0.0046 (5) | 0.0003 (5) | −0.0004 (4) |
C2 | 0.0155 (7) | 0.0135 (7) | 0.0118 (6) | −0.0012 (6) | 0.0007 (6) | −0.0013 (6) |
C3 | 0.0145 (7) | 0.0146 (7) | 0.0131 (6) | −0.0003 (6) | 0.0022 (6) | −0.0016 (6) |
C4 | 0.0155 (8) | 0.0215 (7) | 0.0139 (6) | 0.0049 (7) | 0.0014 (6) | 0.0008 (6) |
O9 | 0.0287 (6) | 0.0148 (5) | 0.0114 (4) | −0.0004 (5) | 0.0058 (5) | −0.0019 (4) |
O8 | 0.0178 (6) | 0.0243 (6) | 0.0139 (5) | 0.0034 (5) | −0.0011 (5) | 0.0013 (5) |
C1—C5 | 1.5147 (19) | O10—H10 | 0.857 |
C1—O7 | 1.4782 (18) | O7—C2 | 1.3417 (16) |
C1—C4 | 1.528 (2) | C2—C3 | 1.521 (2) |
C1—H1 | 0.975 | C2—O8 | 1.2126 (18) |
C5—C6 | 1.518 (2) | C3—C4 | 1.519 (2) |
C5—O10 | 1.4285 (17) | C3—O9 | 1.4107 (16) |
C5—H5 | 0.969 | C3—H3 | 0.965 |
C6—O11 | 1.4357 (18) | C4—H41 | 0.991 |
C6—H61 | 0.975 | C4—H42 | 0.971 |
C6—H62 | 1.008 | O9—H9 | 0.880 |
O11—H11 | 0.855 | ||
C5—C1—O7 | 108.12 (12) | C5—O10—H10 | 111.2 |
C5—C1—C4 | 114.28 (12) | C1—O7—C2 | 110.07 (11) |
O7—C1—C4 | 104.57 (10) | O7—C2—C3 | 110.84 (12) |
C5—C1—H1 | 109.4 | O7—C2—O8 | 121.20 (14) |
O7—C1—H1 | 107.7 | C3—C2—O8 | 127.95 (13) |
C4—C1—H1 | 112.4 | C2—C3—C4 | 102.58 (11) |
C1—C5—C6 | 111.45 (13) | C2—C3—O9 | 111.85 (12) |
C1—C5—O10 | 109.23 (11) | C4—C3—O9 | 111.85 (12) |
C6—C5—O10 | 109.87 (11) | C2—C3—H3 | 107.2 |
C1—C5—H5 | 107.4 | C4—C3—H3 | 110.7 |
C6—C5—H5 | 109.5 | O9—C3—H3 | 112.1 |
O10—C5—H5 | 109.3 | C1—C4—C3 | 103.33 (12) |
C5—C6—O11 | 111.07 (12) | C1—C4—H41 | 109.9 |
C5—C6—H61 | 109.8 | C3—C4—H41 | 109.6 |
O11—C6—H61 | 106.9 | C1—C4—H42 | 111.2 |
C5—C6—H62 | 108.0 | C3—C4—H42 | 112.6 |
O11—C6—H62 | 110.1 | H41—C4—H42 | 110.1 |
H61—C6—H62 | 111.0 | C3—O9—H9 | 109.5 |
C6—O11—H11 | 108.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O11i | 0.86 | 1.83 | 2.6814 (15) | 177 |
O11—H11···O8ii | 0.86 | 1.90 | 2.7384 (13) | 166 |
O9—H9···O10iii | 0.88 | 1.83 | 2.6966 (14) | 167 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, −y+1, z+1/2; (iii) −x+1/2, −y+1, z−1/2. |
Footnotes
‡Visiting Scientist at the Department of Chemical Crystallography, Chemical Research Laboratory, Mansfield Road, Oxford OX1 3TA England
Acknowledgements
Financial support from the EPSRC (to DH) is gratefully acknowledged.
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