6-De­oxy-α-l-talopyran­ose

Booth, K.V.; Jenkinson, S.F.; Fleet, G.W.J.; Gullapalli, P.; Yoshihara, A.; Izumori, K.; Watkin, D.J.

doi:10.1107/S1600536808019582

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1385

doi:10.1107/S1600536808019582

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6-Deoxy-α-L-talopyranose

K. Victoria Booth,^a ^* Sarah F. Jenkinson,^a George W. J. Fleet,^a Pushpakiran Gullapalli,^b Akihide Yoshihara,^b Ken Izumori ^b and David J. Watkin ^c

^aDepartment of Organic Chemistry, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, England, ^bRare Sugar Research Centre, Kagawa University, 2393 Miki-cho, Kita-gun, Kagawa 761-0795, Japan, and ^cDepartment of Chemical Crystallography, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, England
^*Correspondence e-mail: victoria.booth@chem.ox.ac.uk

(Received 25 June 2008; accepted 27 June 2008; online 5 July 2008)

X-ray crystallography showed that the title compound, C₆H₁₂O₅, crystallizes in the α-pyranose form with the six-membered ring in a chair conformation. The crystal structure exists as a three-dimensional hydrogen-bonded network of molecules with each molecule acting as a donor and aceptor for four hydrogen bonds. The absolute configuration was determined by the use of L-fucose as starting material.

Related literature

For related literature, see: Beadle et al. (1992 ); Izumori (2002 , 2006 ); Granstrom et al. (2004 ); Yoshihara et al. (2008 ).

Experimental

Crystal data

C₆H₁₂O₅
M_r = 164.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.4939 (3) Å
b = 7.4874 (4) Å
c = 14.8382 (8) Å
V = 721.47 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 150 K
0.25 × 0.25 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997 ) T_min = 0.97, T_max = 1.00 (expected range = 0.967–0.997)
4390 measured reflections
968 independent reflections
863 reflections with I > 2.0σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.072
S = 1.03
968 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H7⋯O1ⁱ	0.81	2.04	2.818 (2)	162
O1—H8⋯O10	0.82	1.98	2.740 (2)	156
O10—H10⋯O9ⁱ	0.84	1.85	2.686 (2)	177
O11—H1⋯O4ⁱⁱ	0.87	1.94	2.812 (2)	177
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: COLLECT (Nonius, 1997–2001 ).; 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, I. DOI: 10.1107/S1600536808019582/lh2652sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019582/lh2652Isup2.hkl

checkCIF report

Comment top

The range of rare sugars that are now readily available has increased in recent years due to both chemical (Beadle et al., 1992) and biotechnological (Izumori, 2006; Izumori, 2002; Granstrom et al., 2004) advances. The methodology developed by Izumori et al. for the interconversion of tetroses, pentoses and hexoses by enzymatic oxidation, inversion at C3 with a single epimerase, and reduction to the aldose has been seen to be generally applicable for the 1-deoxy ketohexoses (Yoshihara et al., 2008) in large amounts in water.

The Izumoring method is demonstrated here with the synthesis of 6-deoxy-L-talose 3 from L-fucose 1(Fig. 1) by a series of isomerizations. Firstly, using D-arabinose isomerase, L-fucose was isomerized to 6-deoxy-L-tagatose 2 and then using L-rhamnose isomerase this was further isomerized to give 6-deoxy-L-talose 3.

6-Deoxy-L-talose crystallizes solely in the α-pyranose form (Fig. 2). The absolute configuration was determined from the starting material. The crystal exists as an hydrogen bonded network with each molecule acting as a donor and acceptor for 4 hydrogen bonds. Non-conventional hydrogen bonds have been ignored.

Related literature top

For related literature, see: Beadle et al. (1992); Izumori (2002, 2006); Granstrom et al. (2004); Yoshihara et al. (2008).

Experimental top

The title compound was recrystallized from methanol: m.p. 120–123°C; [α]_D²⁰ -18.6 (c, 0.94 in H₂O).

Computing details top

Data collection: COLLECT (Nonius, 1997-2001).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); 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 (Betteridge et al., 2003).

Figures top

	Fig. 1. Synthetic scheme.
	Fig. 2. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
	Fig. 3. Packing diagram of the title compound projected along the a-axis.

(I) top

Crystal data top

C₆H₁₂O₅	F(000) = 352
M_r = 164.16	D_x = 1.511 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 890 reflections
a = 6.4939 (3) Å	θ = 5–27°
b = 7.4874 (4) Å	µ = 0.13 mm⁻¹
c = 14.8382 (8) Å	T = 150 K
V = 721.47 (6) Å³	Plate, colourless
Z = 4	0.25 × 0.25 × 0.02 mm

Data collection top

Nonius KappaCCD diffractometer	863 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 27.5°, θ_min = 5.2°
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)	h = −8→8
T_min = 0.97, T_max = 1.00	k = −9→9
4390 measured reflections	l = −19→19
968 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)] = 0.029	H-atom parameters constrained
wR(F²) = 0.072	Method = Modified Sheldrick w = 1/[σ²(F²) + ( 0.04P)² + 0.04P] , where P = (max(F_o²,0) + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.000184
968 reflections	Δρ_max = 0.24 e Å⁻³
100 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints

Crystal data top

C₆H₁₂O₅	V = 721.47 (6) Å³
M_r = 164.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.4939 (3) Å	µ = 0.13 mm⁻¹
b = 7.4874 (4) Å	T = 150 K
c = 14.8382 (8) Å	0.25 × 0.25 × 0.02 mm

Data collection top

Nonius KappaCCD diffractometer	968 independent reflections
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)	863 reflections with I > 2.0σ(I)
T_min = 0.97, T_max = 1.00	R_int = 0.037
4390 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.03	Δρ_max = 0.24 e Å⁻³
968 reflections	Δρ_min = −0.21 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.95002 (16)	0.08900 (18)	0.35376 (7)	0.0210
C2	0.7416 (2)	0.1250 (2)	0.32982 (10)	0.0175
C3	0.6113 (3)	0.1509 (3)	0.41551 (10)	0.0188
O4	0.65011 (17)	0.31964 (16)	0.45740 (7)	0.0183
C5	0.6150 (2)	0.4717 (2)	0.39897 (10)	0.0194
C6	0.6412 (3)	0.6382 (3)	0.45454 (12)	0.0271
C7	0.7657 (2)	0.4593 (2)	0.32003 (10)	0.0187
C8	0.7208 (2)	0.2889 (3)	0.26846 (10)	0.0186
O9	0.85143 (18)	0.26675 (18)	0.19178 (7)	0.0243
O10	0.97297 (17)	0.45445 (18)	0.35319 (8)	0.0232
O11	0.40458 (18)	0.1333 (2)	0.39115 (8)	0.0254
H21	0.6937	0.0193	0.2985	0.0197*
H31	0.6474	0.0567	0.4621	0.0197*
H51	0.4756	0.4675	0.3773	0.0236*
H61	0.6179	0.7441	0.4188	0.0406*
H62	0.5480	0.6346	0.5057	0.0398*
H63	0.7791	0.6452	0.4743	0.0401*
H71	0.7508	0.5628	0.2786	0.0214*
H81	0.5761	0.2938	0.2475	0.0221*
H7	0.8826	0.3664	0.1753	0.0374*
H8	0.9866	0.1914	0.3632	0.0333*
H10	1.0243	0.5538	0.3399	0.0350*
H1	0.3258	0.1436	0.4383	0.0408*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0198 (5)	0.0204 (7)	0.0229 (6)	0.0030 (5)	−0.0010 (5)	−0.0005 (5)
C2	0.0184 (7)	0.0188 (9)	0.0153 (7)	−0.0001 (8)	−0.0013 (6)	−0.0015 (6)
C3	0.0209 (8)	0.0186 (9)	0.0169 (7)	−0.0037 (7)	0.0005 (6)	−0.0021 (7)
O4	0.0223 (5)	0.0178 (7)	0.0150 (5)	−0.0008 (5)	−0.0006 (5)	0.0007 (5)
C5	0.0220 (8)	0.0184 (9)	0.0179 (7)	0.0019 (8)	−0.0015 (7)	0.0002 (7)
C6	0.0378 (10)	0.0202 (10)	0.0232 (8)	0.0022 (9)	0.0025 (9)	−0.0040 (7)
C7	0.0183 (7)	0.0202 (9)	0.0176 (7)	0.0031 (7)	0.0006 (7)	0.0029 (7)
C8	0.0197 (7)	0.0212 (10)	0.0149 (7)	0.0011 (7)	0.0013 (6)	−0.0005 (7)
O9	0.0335 (6)	0.0213 (7)	0.0180 (5)	0.0043 (6)	0.0087 (5)	0.0025 (5)
O10	0.0195 (5)	0.0195 (7)	0.0306 (6)	−0.0026 (5)	−0.0015 (5)	0.0023 (6)
O11	0.0199 (5)	0.0331 (8)	0.0233 (5)	−0.0074 (6)	0.0028 (5)	−0.0047 (6)

Geometric parameters (Å, º) top

O1—C2	1.4250 (19)	C6—H61	0.966
O1—H8	0.815	C6—H62	0.971
C2—C3	1.540 (2)	C6—H63	0.944
C2—C8	1.534 (2)	C7—C8	1.516 (2)
C2—H21	0.969	C7—O10	1.4334 (19)
C3—O4	1.430 (2)	C7—H71	0.994
C3—O11	1.3965 (19)	C8—O9	1.4288 (18)
C3—H31	1.015	C8—H81	0.990
O4—C5	1.449 (2)	O9—H7	0.811
C5—C6	1.504 (2)	O10—H10	0.839
C5—C7	1.529 (2)	O11—H1	0.870
C5—H51	0.962

C2—O1—H8	98.1	C5—C6—H62	109.6
O1—C2—C3	109.88 (12)	H61—C6—H62	110.8
O1—C2—C8	112.50 (13)	C5—C6—H63	108.9
C3—C2—C8	109.93 (14)	H61—C6—H63	105.9
O1—C2—H21	105.7	H62—C6—H63	110.5
C3—C2—H21	108.8	C5—C7—C8	108.34 (14)
C8—C2—H21	109.9	C5—C7—O10	109.84 (12)
C2—C3—O4	111.93 (14)	C8—C7—O10	109.43 (14)
C2—C3—O11	107.62 (12)	C5—C7—H71	111.3
O4—C3—O11	111.43 (15)	C8—C7—H71	109.0
C2—C3—H31	110.4	O10—C7—H71	108.9
O4—C3—H31	106.1	C2—C8—C7	110.89 (12)
O11—C3—H31	109.4	C2—C8—O9	109.12 (13)
C3—O4—C5	113.97 (11)	C7—C8—O9	112.67 (13)
O4—C5—C6	107.79 (12)	C2—C8—H81	107.4
O4—C5—C7	108.05 (13)	C7—C8—H81	108.0
C6—C5—C7	113.45 (14)	O9—C8—H81	108.5
O4—C5—H51	108.8	C8—O9—H7	106.4
C6—C5—H51	108.5	C7—O10—H10	105.7
C7—C5—H51	110.1	C3—O11—H1	110.4
C5—C6—H61	111.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H7···O1ⁱ	0.81	2.04	2.818 (2)	162
O1—H8···C7	0.82	2.55	3.061 (2)	122
O1—H8···O10	0.82	1.98	2.740 (2)	156
O10—H10···O9ⁱ	0.84	1.85	2.686 (2)	177
O11—H1···O4ⁱⁱ	0.87	1.94	2.812 (2)	177

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₁₂O₅
M_r	164.16
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.4939 (3), 7.4874 (4), 14.8382 (8)
V (Å³)	721.47 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.25 × 0.25 × 0.02

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)
T_min, T_max	0.97, 1.00
No. of measured, independent and observed [I > 2.0σ(I)] reflections	4390, 968, 863
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.072, 1.03
No. of reflections	968
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: COLLECT (Nonius, 1997-2001)., DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H7···O1ⁱ	0.81	2.04	2.818 (2)	162
O1—H8···O10	0.82	1.98	2.740 (2)	156
O10—H10···O9ⁱ	0.84	1.85	2.686 (2)	177
O11—H1···O4ⁱⁱ	0.87	1.94	2.812 (2)	177

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1.

Acknowledgements

We gratefully acknowledge the Oxford University Chemical Crystallography service for use of the instruments. This work was supported in part by the Program for Promotion of Basic Research Activities for Innovative Biosciences (PROBRAIN).

References

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