2,5-Di-O-acetyl-3-C-methyl-d-lyxono-1,4-lactone

Bream, R.; Watkin, D.; Soengas, R.; Eastwick-Field, V.; Fleet, G.W.J.

doi:10.1107/S1600536806004211

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 3| March 2006| Pages o977-o979

https://doi.org/10.1107/S1600536806004211

2,5-Di-O-acetyl-3-C-methyl-D-lyxono-1,4-lactone

Richard Bream,^a David Watkin,^a Raquel Soengas,^b Vanessa Eastwick-Field ^c and George W. J. Fleet ^b ^*

^aChemical Crystallography, Central Chemistry Laboratory, University of Oxford, Oxford OX1 3TA, England, ^bDepartment of Organic Chemistry, Chemical Research Laboratory, Oxford University, Mansfield Road, Oxford OX1 3TA, England, and ^cCMS Chemicals, 9 Milton Park, Abingdon, Oxfordshire OX14 4RR, England
^*Correspondence e-mail: richard.bream@pmb.ox.ac.uk

(Received 25 January 2006; accepted 3 February 2006; online 8 February 2006)

The structures of both lactones derived from the Kiliani ascension of 2-C-methyl-D-threose were defined by the crystal structure of the title compound, C₁₀H₁₄O₇. The structure consists of hydrogen-bonded ribbons of molecules.

Comment

The Kiliani reaction of ketoses with cyanide, followed by acetonation, has provided a simple and environmentally friendly procedure for the generation of a set of carbohydrate scaffolds with a branched hydroxymethyl group at C-2 (Hotchkiss et al., 2004 ; Soengas et al., 2005 ). Branched sugar lactones bearing a C-2 methyl group may be accessed either by a Kiliani reaction on 1-deoxyketoses or by treatment of an Amadori ketose with aqueous calcium hydroxide (Hotchkiss et al., 2006 ). X-ray crystallographic analysis has been crucial in establishing the structures of the products in these reactions (Punzo et al., 2006 ; Watkin et al., 2005 ; Harding et al., 2005 ). Although these syntheses provide convenient access to C-2 carbon-branched carbohydrates, there are very few reports of sugars with a carbon branch at C-3; a 3-C-methylpentonolactone of unknown stereochemistry has been isolated from cigarette smoke (Schumacher et al., 1977 ) and 3-C-methyl-D-mannose is one of the components of the trisaccharide repeating unit of the polysaccharide from Helicobacter Pylori (Kwon et al., 2004 ).

3-C-Methyl aldonolactones should be accessible through a Kiliani reaction on a branched 2-C-methyl aldose. Reaction of 2-C-methyl-D-threose (1) with aqueous sodium cyanide afforded an inseparable mixture of the C-3-methyl branched lactones (2) and (5); the mixture was treated with an excess of acetic anhydride in pyridine to give a separable mixture of two triacetates (3) and (6) together with a crystalline diacetate (4) (Soengas & Fleet, 2006 ). Determination of the relative stereochemistry of the diacetate (4) as a lyxono-1,4-lactone by X-ray crystallographic analysis (Fig. 1) allowed unambiguous structural assigments of both the triacetates (3) and (6), and thus of the C-3 branched lyxono- (2) and xylono- (5) lactones. The use of 2-C-methyl-D-threose (1) as the starting material in the synthesis defines the absolute configuration of (4). Both C-2 and C-3 branched sugars are likely to increase significantly the range of carbohydrate chirons (Lichtenthaler & Peters, 2004 ) available for the efficient synthesis of complex homochiral targets (Simone et al., 2005 ) and also to provide material for the first time for the study of interactions of such unnatural monosaccharides with biological receptors.

The crystal structure consists of layers of molecules lying perpendicular to the c axis (Fig. 2). Within each layer are interlocking zigzag ribbons of hydrogen-bonded molecules (Fig. 3).

Figure 1
The title compound, with displacement ellipsoids drawn at the 50% probability level. The H atoms are shown as spheres of arbitary radius.

Figure 2
A b-axis projection showing layers of molecules. Dashed lines indicate hydrogen bonds.

Figure 3
A c-axis projection of one layer of molecules, showing the hydrogen-bonded (dashed lines) ribbons lying parallel to b.

Experimental

The material was prepared (Soengas & Fleet, 2006) using a Kiliani reaction. The diacetate (4) was crystallized from chloroform; m.p. 521–523 K, [α]_D²³ +60.0 (c, 1.7 in acetone).

Crystal data

C₁₀H₁₄O₇
M_r = 246.22
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.8524 (1) Å
b = 10.0821 (2) Å
c = 13.1198 (2) Å
V = 1170.95 (3) Å³
Z = 4
D_x = 1.397 Mg m⁻³
Mo Kα radiation
Cell parameters from 1560 reflections
θ = 5–27°
μ = 0.12 mm⁻¹
T = 150 K
Plate, colourless
0.20 × 0.20 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997 )T_min = 0.869, T_max = 0.990
2688 measured reflections
1545 independent reflections
1545 reflections with I > −3.0σ(I)
R_int = 0.009
θ_max = 27.5°
h = −11 → 11
k = −13 → 13
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.073
S = 0.91
1545 reflections
154 parameters
H-atom parameters constrained
Modified Chebychev polynomial (Watkin, 1994 ; Prince, 1982 ) with the coefficients 11.3, 16.9, 8.59, 2.51
(Δ/σ)_max < 0.001
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O16—H8⋯O11ⁱ	0.83	2.11	2.926 (2)	167
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

The H atoms were all 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 = 0.93–0.98 and O—H = 0.82 Å) and displacement parameters [U_iso(H) = 1.2–1.5U_eq of the parent atom], after which they were refined with riding constraints. In the absence of significant anomalous dispersion effects, Friedel pairs were averaged.

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 4, global. DOI: https://doi.org/10.1107/S1600536806004211/cf6489sup1.cif

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S1600536806004211/cf64894sup2.hkl

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.

2,5-Di-O-acetyl-3-C-methyl-D-lyxono-1,4-lactone top

Crystal data top

C₁₀H₁₄O₇	D_x = 1.397 Mg m⁻³
M_r = 246.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1560 reflections
a = 8.8524 (1) Å	θ = 5–27°
b = 10.0821 (2) Å	µ = 0.12 mm⁻¹
c = 13.1198 (2) Å	T = 150 K
V = 1170.95 (3) Å³	Plate, colourless
Z = 4	0.20 × 0.20 × 0.08 mm
F(000) = 520

Data collection top

Nonius KappaCCD diffractometer	1545 reflections with I > −3.0σ(I)
Graphite monochromator	R_int = 0.009
ω scans	θ_max = 27.5°, θ_min = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
T_min = 0.869, T_max = 0.990	k = −13→13
2688 measured reflections	l = −16→16
1545 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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.073	Modified Chebychev polynomial (Watkin, 1994; Prince, 1982) with the coefficients 11.3, 16.9, 8.59, 2.51
S = 0.91	(Δ/σ)_max = 0.000247
1545 reflections	Δρ_max = 0.27 e Å⁻³
154 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
C2	0.86077 (18)	0.77278 (17)	0.32579 (13)	0.0218
C3	0.8007 (2)	0.67351 (18)	0.24961 (15)	0.0246
O4	0.66668 (14)	0.71630 (12)	0.21387 (10)	0.0259
C5	0.63200 (19)	0.84694 (16)	0.25745 (13)	0.0220
C6	0.5579 (2)	0.93071 (18)	0.17730 (14)	0.0265
O7	0.41613 (14)	0.86863 (13)	0.14924 (10)	0.0273
C18	0.3294 (2)	0.94326 (18)	0.08704 (14)	0.0268
O9	0.36545 (17)	1.05300 (14)	0.06062 (12)	0.0388
C10	0.1867 (2)	0.8737 (2)	0.05766 (17)	0.0364
O11	0.85646 (17)	0.57035 (13)	0.22296 (12)	0.0339
O12	1.02057 (13)	0.78292 (13)	0.31932 (9)	0.0252
C13	1.10358 (19)	0.72849 (17)	0.39600 (12)	0.0213
O14	1.04802 (15)	0.66905 (14)	0.46585 (9)	0.0287
C15	1.26726 (19)	0.75652 (18)	0.37875 (14)	0.0268
O16	0.85902 (15)	0.95473 (13)	0.20639 (10)	0.0256
C17	0.7718 (2)	1.00576 (19)	0.37796 (15)	0.0293
C8	0.78459 (19)	0.90227 (16)	0.29387 (14)	0.0213
H21	0.8338	0.7455	0.3966	0.0271*
H51	0.5629	0.8339	0.3181	0.0261*
H61	0.5387	1.0204	0.2023	0.0320*
H62	0.6196	0.9360	0.1157	0.0329*
H101	0.1203	0.9367	0.0301	0.0559*
H102	0.1382	0.8303	0.1174	0.0566*
H103	0.2129	0.8082	0.0082	0.0564*
H151	1.3294	0.6941	0.4221	0.0381*
H152	1.2888	0.8458	0.4011	0.0385*
H153	1.2896	0.7507	0.3076	0.0376*
H171	0.7183	1.0820	0.3511	0.0404*
H172	0.8737	1.0354	0.3990	0.0404*
H173	0.7197	0.9751	0.4386	0.0401*
H8	0.9435	0.9747	0.2287	0.0400*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0173 (7)	0.0227 (7)	0.0255 (7)	−0.0016 (7)	−0.0011 (7)	0.0038 (7)
C3	0.0205 (8)	0.0245 (8)	0.0289 (8)	0.0001 (7)	−0.0023 (7)	0.0031 (7)
O4	0.0213 (6)	0.0218 (5)	0.0345 (6)	0.0015 (5)	−0.0067 (5)	−0.0018 (5)
C5	0.0184 (7)	0.0193 (7)	0.0285 (8)	−0.0002 (6)	−0.0008 (7)	0.0016 (6)
C6	0.0195 (8)	0.0249 (8)	0.0351 (9)	0.0000 (7)	−0.0038 (7)	0.0059 (8)
O7	0.0211 (6)	0.0252 (6)	0.0356 (7)	0.0003 (5)	−0.0058 (5)	0.0068 (6)
C18	0.0248 (8)	0.0275 (8)	0.0282 (8)	0.0058 (7)	−0.0021 (7)	0.0025 (7)
O9	0.0360 (8)	0.0329 (7)	0.0476 (8)	0.0021 (6)	−0.0096 (7)	0.0145 (7)
C10	0.0300 (9)	0.0390 (10)	0.0401 (11)	0.0025 (9)	−0.0114 (9)	0.0041 (9)
O11	0.0305 (7)	0.0262 (6)	0.0450 (8)	0.0085 (6)	−0.0066 (7)	−0.0058 (6)
O12	0.0160 (5)	0.0312 (6)	0.0284 (6)	−0.0025 (5)	−0.0012 (5)	0.0072 (6)
C13	0.0205 (7)	0.0205 (7)	0.0230 (7)	0.0018 (7)	−0.0017 (6)	−0.0030 (7)
O14	0.0258 (6)	0.0351 (7)	0.0254 (6)	0.0045 (6)	0.0011 (5)	0.0060 (6)
C15	0.0192 (8)	0.0318 (9)	0.0292 (8)	0.0006 (7)	−0.0018 (7)	−0.0040 (8)
O16	0.0216 (6)	0.0282 (6)	0.0270 (6)	−0.0028 (5)	0.0012 (5)	0.0085 (5)
C17	0.0312 (10)	0.0249 (8)	0.0318 (9)	−0.0032 (8)	0.0005 (8)	−0.0023 (8)
C8	0.0195 (7)	0.0208 (7)	0.0236 (8)	−0.0022 (6)	0.0012 (7)	0.0044 (7)

Geometric parameters (Å, º) top

C2—C3	1.511 (2)	C10—H101	0.937
C2—O12	1.4208 (19)	C10—H102	0.995
C2—C8	1.528 (2)	C10—H103	0.955
C2—H21	0.997	O12—C13	1.361 (2)
C3—O4	1.347 (2)	C13—O14	1.200 (2)
C3—O11	1.203 (2)	C13—C15	1.493 (2)
O4—C5	1.468 (2)	C15—H151	1.012
C5—C6	1.500 (2)	C15—H152	0.966
C5—C8	1.538 (2)	C15—H153	0.956
C5—H51	1.012	O16—C8	1.425 (2)
C6—O7	1.450 (2)	O16—H8	0.828
C6—H61	0.977	C17—C8	1.523 (3)
C6—H62	0.977	C17—H171	0.969
O7—C18	1.349 (2)	C17—H172	0.990
C18—O9	1.203 (2)	C17—H173	0.970
C18—C10	1.496 (3)

C3—C2—O12	111.00 (14)	H101—C10—H102	109.3
C3—C2—C8	103.26 (14)	C18—C10—H103	107.1
O12—C2—C8	111.20 (14)	H101—C10—H103	111.1
C3—C2—H21	110.4	H102—C10—H103	109.6
O12—C2—H21	108.3	C2—O12—C13	117.67 (13)
C8—C2—H21	112.7	O12—C13—O14	122.97 (15)
C2—C3—O4	109.15 (15)	O12—C13—C15	109.61 (14)
C2—C3—O11	128.36 (17)	O14—C13—C15	127.42 (16)
O4—C3—O11	122.47 (17)	C13—C15—H151	108.9
C3—O4—C5	109.63 (13)	C13—C15—H152	108.8
O4—C5—C6	108.88 (14)	H151—C15—H152	107.6
O4—C5—C8	105.23 (13)	C13—C15—H153	109.7
C6—C5—C8	113.44 (14)	H151—C15—H153	113.5
O4—C5—H51	108.4	H152—C15—H153	108.2
C6—C5—H51	111.1	C8—O16—H8	102.9
C8—C5—H51	109.5	C8—C17—H171	108.5
C5—C6—O7	108.27 (14)	C8—C17—H172	109.9
C5—C6—H61	111.2	H171—C17—H172	107.9
O7—C6—H61	109.5	C8—C17—H173	114.3
C5—C6—H62	111.5	H171—C17—H173	108.6
O7—C6—H62	107.3	H172—C17—H173	107.5
H61—C6—H62	108.9	C5—C8—C2	99.38 (12)
C6—O7—C18	113.90 (14)	C5—C8—C17	114.10 (14)
O7—C18—O9	122.45 (18)	C2—C8—C17	114.82 (15)
O7—C18—C10	112.03 (16)	C5—C8—O16	106.89 (14)
O9—C18—C10	125.51 (18)	C2—C8—O16	109.50 (14)
C18—C10—H101	108.2	C17—C8—O16	111.32 (14)
C18—C10—H102	111.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O16—H8···O11ⁱ	0.83	2.11	2.926 (2)	167

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

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