3-De­oxy-d-galactono-1,4-lactone (3-de­oxy-d-xylo-hexono-1,4-lactone)

Punzo, F.; Watkin, D.J.; Hotchkiss, D.; Fleet, G.W.J.

doi:10.1107/S1600536806008099

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1344-o1346

https://doi.org/10.1107/S1600536806008099

3-Deoxy-D-galactono-1,4-lactone (3-deoxy-D-xylo-hexono-1,4-lactone)

Francesco Punzo,^a ^*‡ David J. Watkin,^b David Hotchkiss ^c and George W. J. Fleet ^c

^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

(Received 17 January 2006; accepted 6 March 2006; online 10 March 2006)

On the basis of the known absolute configuration of 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.

Comment

A number of useful synthetic carbohydrate scaffolds, including several branched carbohydrate lactones (Monneret & Florent, 1994 ) 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 ).

Lactone (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 crystal structure of (1), prepared from galactose and calcium hydroxide, and unambiguously establishes the relative stereochemistry (Fig. 1). The use of D-galactose as starting material defines the absolute configuration 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.

The 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.

Figure 1
The molecular structure of (1), showing displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as small circles of arbitrary radii.

Figure 2
Packing diagram of (1), viewed down the b axis. Hydrogen bonds are shown as dotted lines.

Experimental

The title compound [m.p. 414–415 K, [α]₂₁^D −43.8 (c 1.24 in water)] was synthesized according to Sowden et al. (1957 ) [literature m.p. 415–416 K, [α]₂₅^D −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

C₆H₁₀O₅
M_r = 162.14
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.3320 (2) Å
b = 8.4865 (3) Å
c = 15.7238 (8) Å
V = 711.50 (5) Å³
Z = 4
D_x = 1.514 Mg m⁻³
Mo Kα radiation
Cell parameters from 787 reflections
θ = 5.1–27.5°
μ = 0.13 mm⁻¹
T = 100 K
Prism, colourless
0.60 × 0.50 × 0.40 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997 )T_min = 0.935, T_max = 0.948
1521 measured reflections
942 independent reflections
896 reflections with I > 2σ(I)
R_int = 0.010
θ_max = 27.4°
h = −6 → 6
k = −10 → 10
l = −20 → 20

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.059
S = 1.05
942 reflections
100 parameters
H-atom parameters constrained
w = 1/[σ²(F²) + (0.01P)² + 0.2P] where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max <0.001
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C5	1.5147 (19)
C1—O7	1.4782 (18)
C1—C4	1.528 (2)
C5—C6	1.518 (2)
C5—O10	1.4285 (17)
C6—O11	1.4357 (18)
O7—C2	1.3417 (16)
C2—C3	1.521 (2)
C2—O8	1.2126 (18)
C3—C4	1.519 (2)
C3—O9	1.4107 (16)

C5—C1—O7	108.12 (12)
C5—C1—C4	114.28 (12)
O7—C1—C4	104.57 (10)
C1—C5—C6	111.45 (13)
C1—C5—O10	109.23 (11)
C6—C5—O10	109.87 (11)
C5—C6—O11	111.07 (12)
C1—O7—C2	110.07 (11)
O7—C2—C3	110.84 (12)
O7—C2—O8	121.20 (14)
C3—C2—O8	127.95 (13)
C2—C3—C4	102.58 (11)
C2—C3—O9	111.85 (12)
C4—C3—O9	111.85 (12)
C1—C4—C3	103.33 (12)

Table 2
Hydrogen-bond geometry (Å, °)

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) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

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 [U_iso(H) = 1.2–1.5U_eq(C,O)], after which their positions were refined with riding constraints. In the absence of significant anomalous scattering, Friedel pairs were merged.

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.

Supporting information

Crystal structure: contains datablocks global, 1. DOI: https://doi.org/10.1107/S1600536806008099/ya6281sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S1600536806008099/ya62811sup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 2001).; cell refinement: 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.

3-Deoxy-D-galactono-1,4-lactone (3-deoxy-D-xylo-hexono-1,4-lactone) top

Crystal data top

C₆H₁₀O₅	D_x = 1.514 Mg m⁻³
M_r = 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

Data collection top

Nonius Kappa CCD diffractometer	896 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
ω scans	θ_max = 27.4°, θ_min = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −6→6
T_min = 0.935, T_max = 0.948	k = −10→10
1521 measured reflections	l = −20→20
942 independent reflections

Refinement top

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(F_o²,0) + 2F_c²]/3
S = 1.05	(Δ/σ)_max < 0.001
942 reflections	Δρ_max = 0.18 e Å⁻³
100 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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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