organic compounds
2-C-Methyl-D-lyxono-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
The title compound, C6H10O5, has been crystallized for the first time, allowing the stereochemistry at C-2 and the ring size of the lactone to be firmly established.
Comment
The Kiliani ascension of et al., 2004; Soengas et al., 2005) provides ready access to a new class of branched carbohydrate scaffolds (Lichtenthaler & Peters, 2004; Bols, 1996) with branched carbon chains. Although saccharinic acids, which are 2-C-methyl are formed in very low yields from treatment of or with aqueous calcium hydroxide (Whistler & BeMiller, 1963), it has been shown that significantly higher yields may be obtained from the reaction of lime with (Hotchkiss et al., 2006) derived from the Amadori rearrangement (Hodge, 1955). D-Galactose reacted with dibenzylamine to form the Amadori ketose, (2) (Grunnagel & Haas, 1969), in which the α-configuration at the anomeric position of the pyranose ring has been proved by X-ray crystallographic analysis (Harding et al., 2005). Treatment of (2) with aqueous calcium hydroxide allowed the isolation of a mixture of two epimeric lactones.
(HotchkissThe structure of the minor isomer was confirmed as 2-C-methyl-D-xylono-1,4-lactone, (3), by an X-ray structure of its 3,5-acetonide (Watkin et al., 2005). The major product, 2-C-methyl-D-lyxono-1,4-lactone, (4), initially isolated as an oil, slowly crystallized, allowing the at C-2 and the ring size of the lyxonolactone to be unambiguously assigned by X-ray crystallographic analysis.
Racemic lactone (4) has only been obtained as an oil (Lopez et al., 1984); the enantiomer of (4) has been prepared in low yield from L-sorbose (Ishizu et al., 1972). The of (4) was determined from the use of D-galactose (1) as the starting material.
Experimental
The lactone (4) {m.p. 379–380K, [α]D23 +70.4 (c 0.87 in acetone)} was crystallized by dissolving it in acetone and allowing the slow evaporation of the solvent until colourless block-shaped crystals formed. The multi-scan technique was used to correct for changes in the illuminated volume.
Crystal data
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Data collection
Refinement
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In the absence of significant Uiso(H) = 1.2–1.5Ueq(parent atom)], after which their positions were refined with riding constraints.
Friedel pairs were merged. H atoms were located in a difference density map. Those attached to C atoms were repositioned geometrically. H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å and O—H = 0.82 Å) and isotropic displacement parameters [Data collection: COLLECT (Nonius, 2001); cell DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and 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
10.1107/S1600536805040456/at6059sup1.cif
contains datablocks global, 4. DOI:Structure factors: contains datablock 4. DOI: 10.1107/S1600536805040456/at60594sup2.hkl
The lactone (4) (m.p. 379–380 K, [α]D23 +70.4 (c 0.87 in acetone)) was crystallized by dissolving it in acetone and allowing the slow evaporation of the solvent until colourless block-shaped crystals formed. The multi-scan technique was used to correct for changes in the illuminated volume.
Because the data were collected with molybdenum radiation, there were no measurable anomalous differences, as a consequence of which it was admissible to merge Friedel pairs of reflections. H atoms were seen in a difference density synthesis. 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 = 0.96–0.98, O—H = 0.81–0.88 Å), after which they were refined as riding, with U(H) = 1.2Ueq(C) for those bonded to carbon, and U(H) = 0.05 Å2 for the hydroxy group.
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.C6H10O5 | F(000) = 344 |
Mr = 162.14 | Dx = 1.549 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 1011 reflections |
a = 18.6680 (5) Å | θ = 5–30° |
b = 5.8280 (2) Å | µ = 0.14 mm−1 |
c = 6.3943 (2) Å | T = 120 K |
β = 92.2219 (14)° | Block, colourless |
V = 695.16 (4) Å3 | 0.70 × 0.60 × 0.50 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 1073 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.010 |
ω scans | θmax = 30.0°, θmin = 5.3° |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −25→26 |
Tmin = 0.92, Tmax = 0.93 | k = −7→8 |
1943 measured reflections | l = −8→9 |
1087 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.024 | w = 1/[σ2(F2) + (0.03P)2 + 0.33P] where P = (Fo2,0) + 2Fc2)/3 |
wR(F2) = 0.061 | (Δ/σ)max = 0.000363 |
S = 1.04 | Δρmax = 0.22 e Å−3 |
1087 reflections | Δρmin = −0.16 e Å−3 |
101 parameters | Extinction correction: Larson (1970), equation 22 |
1 restraint | Extinction coefficient: 490 (30) |
Primary atom site location: structure-invariant direct methods |
C6H10O5 | V = 695.16 (4) Å3 |
Mr = 162.14 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 18.6680 (5) Å | µ = 0.14 mm−1 |
b = 5.8280 (2) Å | T = 120 K |
c = 6.3943 (2) Å | 0.70 × 0.60 × 0.50 mm |
β = 92.2219 (14)° |
Nonius KappaCCD diffractometer | 1087 independent reflections |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 1073 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 0.93 | Rint = 0.010 |
1943 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 1 restraint |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.22 e Å−3 |
1087 reflections | Δρmin = −0.16 e Å−3 |
101 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.62534 (6) | −0.0653 (2) | 0.62746 (18) | 0.0118 | |
C2 | 0.62752 (6) | −0.1232 (2) | 0.39310 (18) | 0.0118 | |
C3 | 0.66213 (6) | 0.0885 (2) | 0.29245 (19) | 0.0134 | |
O4 | 0.70639 (5) | 0.18637 (17) | 0.46441 (13) | 0.0153 | |
C5 | 0.68912 (6) | 0.0998 (2) | 0.65261 (19) | 0.0139 | |
O6 | 0.72080 (5) | 0.1571 (2) | 0.81146 (15) | 0.0203 | |
C7 | 0.61246 (7) | 0.2698 (2) | 0.20044 (19) | 0.0160 | |
O8 | 0.56415 (5) | 0.34812 (16) | 0.35384 (15) | 0.0177 | |
O9 | 0.56175 (5) | −0.19459 (17) | 0.29616 (14) | 0.0136 | |
O10 | 0.56216 (4) | 0.05895 (18) | 0.67885 (13) | 0.0138 | |
C11 | 0.63081 (7) | −0.2712 (2) | 0.7718 (2) | 0.0161 | |
H21 | 0.6625 | −0.2465 | 0.3726 | 0.0110* | |
H31 | 0.6924 | 0.0333 | 0.1831 | 0.0132* | |
H71 | 0.6421 | 0.3972 | 0.1576 | 0.0166* | |
H72 | 0.5877 | 0.2039 | 0.0787 | 0.0164* | |
H111 | 0.6312 | −0.2152 | 0.9153 | 0.0203* | |
H112 | 0.6729 | −0.3606 | 0.7480 | 0.0211* | |
H113 | 0.5871 | −0.3629 | 0.7458 | 0.0206* | |
H10 | 0.5535 | 0.1590 | 0.5935 | 0.0169* | |
H8 | 0.5610 | 0.4976 | 0.3450 | 0.0229* | |
H9 | 0.5301 | −0.0909 | 0.3159 | 0.0174* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0105 (5) | 0.0117 (6) | 0.0132 (5) | −0.0010 (4) | 0.0008 (4) | 0.0004 (4) |
C2 | 0.0109 (5) | 0.0117 (5) | 0.0129 (5) | 0.0003 (4) | 0.0003 (4) | −0.0008 (5) |
C3 | 0.0143 (5) | 0.0141 (6) | 0.0118 (5) | −0.0018 (5) | 0.0012 (4) | −0.0007 (5) |
O4 | 0.0148 (4) | 0.0181 (5) | 0.0132 (4) | −0.0051 (4) | 0.0012 (3) | 0.0002 (4) |
C5 | 0.0116 (5) | 0.0155 (6) | 0.0147 (5) | −0.0011 (5) | 0.0021 (4) | 0.0006 (5) |
O6 | 0.0181 (4) | 0.0271 (6) | 0.0154 (4) | −0.0064 (4) | −0.0016 (3) | −0.0016 (4) |
C7 | 0.0210 (6) | 0.0135 (6) | 0.0134 (5) | −0.0012 (5) | 0.0015 (4) | 0.0010 (5) |
O8 | 0.0217 (5) | 0.0109 (5) | 0.0209 (4) | 0.0011 (4) | 0.0054 (3) | 0.0021 (4) |
O9 | 0.0116 (4) | 0.0115 (4) | 0.0174 (4) | 0.0003 (3) | −0.0015 (3) | −0.0023 (3) |
O10 | 0.0124 (4) | 0.0140 (4) | 0.0152 (4) | 0.0011 (4) | 0.0026 (3) | 0.0005 (4) |
C11 | 0.0176 (6) | 0.0147 (6) | 0.0160 (5) | 0.0006 (5) | 0.0007 (4) | 0.0039 (5) |
C1—C2 | 1.5382 (16) | C5—O6 | 1.2027 (15) |
C1—C5 | 1.5342 (17) | C7—O8 | 1.4327 (16) |
C1—O10 | 1.4329 (14) | C7—H71 | 0.972 |
C1—C11 | 1.5150 (18) | C7—H72 | 0.969 |
C2—C3 | 1.5448 (19) | O8—H8 | 0.875 |
C2—O9 | 1.4163 (14) | O9—H9 | 0.858 |
C2—H21 | 0.983 | O10—H10 | 0.811 |
C3—O4 | 1.4652 (15) | C11—H111 | 0.974 |
C3—C7 | 1.5098 (18) | C11—H112 | 0.960 |
C3—H31 | 0.971 | C11—H113 | 0.984 |
O4—C5 | 1.3553 (15) | ||
C2—C1—C5 | 100.95 (9) | C1—C5—O4 | 110.53 (10) |
C2—C1—O10 | 112.80 (9) | C1—C5—O6 | 128.09 (11) |
C5—C1—O10 | 107.55 (10) | O4—C5—O6 | 121.36 (12) |
C2—C1—C11 | 114.56 (10) | C3—C7—O8 | 110.46 (10) |
C5—C1—C11 | 113.52 (10) | C3—C7—H71 | 107.3 |
O10—C1—C11 | 107.29 (9) | O8—C7—H71 | 109.2 |
C1—C2—C3 | 104.94 (10) | C3—C7—H72 | 107.6 |
C1—C2—O9 | 115.82 (10) | O8—C7—H72 | 112.5 |
C3—C2—O9 | 114.94 (10) | H71—C7—H72 | 109.6 |
C1—C2—H21 | 109.5 | C7—O8—H8 | 108.4 |
C3—C2—H21 | 103.8 | C2—O9—H9 | 108.6 |
O9—C2—H21 | 107.2 | C1—O10—H10 | 110.7 |
C2—C3—O4 | 103.36 (9) | C1—C11—H111 | 107.8 |
C2—C3—C7 | 117.44 (10) | C1—C11—H112 | 111.7 |
O4—C3—C7 | 109.87 (11) | H111—C11—H112 | 110.7 |
C2—C3—H31 | 107.5 | C1—C11—H113 | 106.9 |
O4—C3—H31 | 110.0 | H111—C11—H113 | 108.5 |
C7—C3—H31 | 108.5 | H112—C11—H113 | 110.9 |
C3—O4—C5 | 112.01 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O8 | 0.81 | 1.90 | 2.6770 (13) | 159 |
O8—H8···O9i | 0.88 | 1.82 | 2.6906 (14) | 172 |
O9—H9···O10ii | 0.86 | 1.93 | 2.7547 (13) | 160 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C6H10O5 |
Mr | 162.14 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 120 |
a, b, c (Å) | 18.6680 (5), 5.8280 (2), 6.3943 (2) |
β (°) | 92.2219 (14) |
V (Å3) | 695.16 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.70 × 0.60 × 0.50 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.92, 0.93 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1943, 1087, 1073 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.061, 1.04 |
No. of reflections | 1087 |
No. of parameters | 101 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.16 |
Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.
C1—C2 | 1.5382 (16) | C3—O4 | 1.4652 (15) |
C1—C5 | 1.5342 (17) | C3—C7 | 1.5098 (18) |
C1—O10 | 1.4329 (14) | O4—C5 | 1.3553 (15) |
C1—C11 | 1.5150 (18) | C5—O6 | 1.2027 (15) |
C2—C3 | 1.5448 (19) | C7—O8 | 1.4327 (16) |
C2—O9 | 1.4163 (14) | ||
C2—C1—C5 | 100.95 (9) | C2—C3—O4 | 103.36 (9) |
C2—C1—O10 | 112.80 (9) | C2—C3—C7 | 117.44 (10) |
C5—C1—O10 | 107.55 (10) | O4—C3—C7 | 109.87 (11) |
C2—C1—C11 | 114.56 (10) | C3—O4—C5 | 112.01 (10) |
C5—C1—C11 | 113.52 (10) | C1—C5—O4 | 110.53 (10) |
O10—C1—C11 | 107.29 (9) | C1—C5—O6 | 128.09 (11) |
C1—C2—C3 | 104.94 (10) | O4—C5—O6 | 121.36 (12) |
C1—C2—O9 | 115.82 (10) | C3—C7—O8 | 110.46 (10) |
C3—C2—O9 | 114.94 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O8 | 0.81 | 1.90 | 2.6770 (13) | 159 |
O8—H8···O9i | 0.88 | 1.82 | 2.6906 (14) | 172 |
O9—H9···O10ii | 0.86 | 1.93 | 2.7547 (13) | 160 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y, −z+1. |
Footnotes
‡Visiting Scientist at the Department of Chemical Crystallography, Chemical Research Laboratory, Mansfield Road, Oxford OX1 3TA England
Acknowledgements
Financial support from EPSRC (to DH) is acknowledged.
References
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The Kiliani ascension of ketoses (Hotchkiss et al., 2004; Soengas et al., 2005) provides ready access to a new class of branched carbohydrate scaffolds (Lichtenthaler & Peters, 2004; Bols, 1996) with branched carbon chains. Although saccharinic acids - which are 2-C-methyl aldonic acids - are formed in very low yields from treatment of aldoses or ketoses with aqueous calcium hydroxide (Whistler & BeMiller, 1963), it has been shown that significantly higher yields may be obtained from the reaction of lime with ketoses (Hotchkiss et al., 2006) derived from the Amadori rearrangement (Hodge, 1955). d-Galactose reacted with dibenzylamine to form the Amadori ketose (2) (Grunnagel & Haas, 1969), in which the α-configuration at the anomeric position of the pyranose ring has been proved by X-ray crystallographic analysis (Harding et al., 2005). Treatment of (2) with aqueous calcium hydroxide allowed the isolation of a mixture of two epimeric lactones.
Table 1.
The structure of the minor isomer was confirmed as 2-C-methyl-d-xylono-1,4-lactone (3) by an X-ray structure of its 3,5-acetonide (Watkin et al., 2005). The major product 2-C-methyl-d-lyxono-1,4-lactone (4), initially isolated as an oil, slowly crystallized allowing the relative configuration at C-2 and the ring size of the lyxonolactone to be unambiguously assigned by X-ray crystallographic analysis.
Figure 1.
Racemic lactone (4) has only been obtained as an oil (Lopez et al., 1984); the enantiomer of (4) has been prepared in low yield from l-sorbose (Ishizu et al., 1982 or 1972). The absolute configuration of (4) is determined from the use of d-galactose (1) as the starting material.
Figure 2.