1,2:3,4-Di-O-isopropyl­idene-β-d-psicofuran­ose

Watkin, D.J.; Glawar, A.F.G.; Soengas, R.; Izumori, K.; Wormald, M.R.; Dwek, R.A.; Fleet, G.W.J.

doi:10.1107/S1600536805025572

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 9| September 2005| Pages o2949-o2951

https://doi.org/10.1107/S1600536805025572

1,2:3,4-Di-O-isopropylidene-β-D-psicofuranose

David J Watkin,^a ^* Andreas F. G. Glawar,^a Raquel Soengas,^b Ken Izumori,^c Mark R. Wormald,^d Raymond A. Dwek ^d and George W. J. Fleet ^b

^aDepartment of Chemical Crystallography, Chemical Research Laboratory, Oxford University, Mansfield Road, Oxford OX1 3TA, England, ^bDepartment of Organic Chemistry, Chemical Research Laboratory, Oxford University, Mansfield Road, Oxford OX1 3TA, England, ^cRare Sugar Research Centre, Kagawa University, Mikicho, Kagawa 761-0795 Japan, and ^dGlycobiology Institute, Department of Biochemistry, Oxford University, South Parks Road, Oxford OX1 3QU, England
^*Correspondence e-mail: david.watkin@chem.ox.ac.uk

(Received 5 August 2005; accepted 10 August 2005; online 17 August 2005)

The crystal structure of the title diacetone psicose, C₁₂H₂₀O₆, establishes the stereochemistry of the anomeric spiroacetal 1,2:3,4-di-O-isopropylidene-β-D-psicofuranose. The structure consists of columns of molecules linked by hydrogen bonds into chains [O⋯O 2.962 (2) Å] lying parallel to the a axis.

Comment

Izumoring, a combination of enzymic epimerizations of ketohexoses combined with microbial oxidation–reduction procedures, can provide access to any hexose in substantial quantity via environmentally friendly procedures (Granstrom et al., 2004 ; Izumori, 2002 ). The rare sugar D-psicose, (1), is now available for the first time in multi-kilogram quantities from the equilibration of D-fructose by D-tagatose 3-epimerase (Takeshita et al., 2000 ; Itoh & Izumori, 1996 ; Itoh et al., 1995 ). Although the main purpose of large-scale production of rare sugars such as D-psicose is for their use in food technology (Sun et al., 2004 , 2005 ), such studies will significantly increase the number of sugar chirons (Lichtenthaler & Peters, 2004 ; Soengas, Izumori et al., 2005 ).

Crystalline diacetonides of carbohydrates are among the most common chiral building blocks in organic synthesis (Bols, 1996 ). The first report of the reaction of psicose with acetone was the formation of a furanose diacetonide from L-psicose (Steiger & Reichstein, 1935 ); the reaction of D-psicose, (1), with acetone gave an enantiomeric diacetonide, (2) (Steiger & Reichstein, 1936 ), with no indication of the chemistry at the anomeric position. All other syntheses of the furanose diacetonide, (2), have been multi-step procedures starting from a pyranose diacetonide of fructose. The original procedure for the preparation of (2) from D-fructose (James et al., 1967 ) has been significantly improved (James et al., 1967; Cree & Perlin, 1968 ; Tipson et al., 1971 ). The diacetonide, (2), has been used as a starting material for the synthesis of nucleosides (Prisbe et al., 1976 ) and imino sugars (Joseph et al., 2002 ). There is no report in any of the numerous previous papers of any attempt to determine the anomeric configuration of the spiro-acetal functionality in (2). In recent studies, it was found that treatment of psicose (1) with acetone in the presence of acid afforded the easily crystallized diacetone psicose, (2) (Soengas, Wormald et al., 2005 ), in good yield. The present report of the crystal structure of (2) unequivocally establishes the anomeric configuration of the diacetonide, (3), as the β-form (Fig. 1).

The structure of (2) consists of columns of molecules linked by hydrogen bonds into chains [O⋯O = 2.962 (2) Å] lying parallel to the a axis (Fig. 2). Contacts between the chains are determined largely by the methyl groups.

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

Figure 2
A projection along the c axis of the crystal structure of the title compound, showing chains of molecules lying parallel to the a axis. Hydrogen bonds are shown as dotted lines.

Experimental

The title material, (2) (Soengas, Wormald et al., 2005), was crystallized from 333–353 K petroleum ether.

Crystal data

C₁₂H₂₀O₆
M_r = 260.29
Orthorhombic, C 222₁
a = 7.5915 (2) Å
b = 20.1407 (6) Å
c = 17.5607 (6) Å
V = 2685.00 (14) Å³
Z = 8
D_x = 1.288 Mg m⁻³
Mo Kα radiation
Cell parameters from 1674 reflections
θ = 5–27°
μ = 0.10 mm⁻¹
T = 190 K
Prism, colourless
0.45 × 0.15 × 0.15 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω scans
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997 )T_min = 0.86, T_max = 0.98
9365 measured reflections
1721 independent reflections
1721 reflections with I > 3σ(I)
R_int = 0.030
θ_max = 27.5°
h = −9 → 9
k = −25 → 25
l = −22 → 22

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.078
S = 0.94
1721 reflections
163 parameters
H-atom parameters constrained
w = 1/[σ²(F²) + (0.04P)² + 0.76P] where P = (max(F_o²,0) + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H1⋯O8ⁱ	0.84	2.19	2.962 (2)	152
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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. 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 in order to regularize their geometry [C—H distances in the range 0.93–98 Å and O—H = 0.82 Å, and U_iso(H) in the range 1.2–1.5U_eq of the adjacent atom], after which they were refined with riding constraints.

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, 2. DOI: https://doi.org/10.1107/S1600536805025572/hg6223sup1.cif

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S1600536805025572/hg62232sup2.hkl

Computing details top

Data collection: COLLECT. (Nonius, 1997-2001).; 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.

1,2:3,4-Di-O-isopropylidene-β-D-psicofuranose top

Crystal data top

C₁₂H₂₀O₆	F(000) = 1120
M_r = 260.29	D_x = 1.288 Mg m⁻³
Orthorhombic, C222₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 1674 reflections
a = 7.5915 (2) Å	θ = 5–27°
b = 20.1407 (6) Å	µ = 0.10 mm⁻¹
c = 17.5607 (6) Å	T = 190 K
V = 2685.00 (14) Å³	Prism, colourless
Z = 8	0.45 × 0.15 × 0.15 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	1721 reflections with I > −3σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 5.3°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −9→9
T_min = 0.86, T_max = 0.98	k = −25→25
9365 measured reflections	l = −22→22
1721 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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F²) + (0.04P)² + 0.76P] where P = (max(F_o²,0) + 2F_c²)/3
S = 0.94	(Δ/σ)_max = 0.000268
1721 reflections	Δρ_max = 0.18 e Å⁻³
163 parameters	Δρ_min = −0.17 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	0.9879 (2)	0.86900 (8)	0.45535 (9)	0.0289
C2	0.8171 (2)	0.89925 (9)	0.48595 (11)	0.0326
C3	0.6934 (2)	0.84018 (8)	0.49965 (10)	0.0306
C4	0.7929 (2)	0.78036 (8)	0.47003 (10)	0.0275
O5	0.97603 (15)	0.79999 (5)	0.47083 (6)	0.0275
C6	0.7334 (2)	0.75971 (9)	0.39077 (10)	0.0337
O7	0.8303 (2)	0.70508 (7)	0.36253 (8)	0.0469
O8	0.68145 (18)	0.83598 (6)	0.58096 (7)	0.0376
C9	0.7244 (3)	0.89956 (10)	0.61173 (12)	0.0420
O10	0.84906 (18)	0.92652 (7)	0.55968 (8)	0.0444
C11	0.5620 (3)	0.94323 (12)	0.61528 (16)	0.0624
C12	0.8129 (5)	0.88883 (13)	0.68779 (13)	0.0715
O13	1.00256 (16)	0.88126 (6)	0.37606 (7)	0.0345
C14	1.1874 (2)	0.88150 (11)	0.35570 (11)	0.0394
O15	1.28119 (17)	0.88358 (7)	0.42634 (8)	0.0435
C16	1.1595 (2)	0.89624 (9)	0.48621 (11)	0.0339
C17	1.2359 (3)	0.81797 (12)	0.31560 (12)	0.0549
C18	1.2212 (3)	0.94316 (13)	0.30907 (15)	0.0683
H21	0.7694	0.9328	0.4502	0.0469*
H31	0.5761	0.8468	0.4764	0.0423*
H41	0.7800	0.7421	0.5053	0.0377*
H61	0.6070	0.7465	0.3941	0.0480*
H62	0.7479	0.7987	0.3569	0.0483*
H111	0.5982	0.9867	0.6347	0.1113*
H112	0.5147	0.9473	0.5645	0.1113*
H113	0.4766	0.9217	0.6485	0.1119*
H121	0.8409	0.9325	0.7088	0.1258*
H122	0.7326	0.8657	0.7212	0.1269*
H123	0.9185	0.8621	0.6796	0.1264*
H161	1.1489	0.9442	0.4944	0.0481*
H162	1.1984	0.8720	0.5333	0.0472*
H171	1.3606	0.8208	0.3027	0.0983*
H172	1.1677	0.8152	0.2679	0.0984*
H173	1.2098	0.7803	0.3489	0.0988*
H181	1.3447	0.9462	0.2985	0.1209*
H182	1.1572	0.9398	0.2621	0.1211*
H183	1.1845	0.9819	0.3380	0.1212*
H1	0.9352	0.7080	0.3775	0.0833*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0298 (8)	0.0252 (8)	0.0317 (9)	−0.0004 (7)	−0.0024 (7)	0.0033 (7)
C2	0.0307 (9)	0.0282 (9)	0.0390 (10)	0.0043 (8)	−0.0006 (8)	0.0047 (8)
C3	0.0288 (8)	0.0322 (9)	0.0307 (8)	0.0018 (8)	−0.0027 (8)	−0.0006 (7)
C4	0.0269 (8)	0.0287 (8)	0.0270 (8)	−0.0032 (7)	−0.0016 (7)	0.0003 (7)
O5	0.0266 (6)	0.0228 (5)	0.0331 (6)	0.0004 (5)	−0.0027 (5)	0.0015 (5)
C6	0.0309 (9)	0.0389 (10)	0.0314 (9)	−0.0032 (8)	−0.0027 (7)	−0.0031 (8)
O7	0.0438 (8)	0.0537 (8)	0.0432 (8)	0.0008 (7)	−0.0022 (7)	−0.0204 (6)
O8	0.0509 (8)	0.0301 (6)	0.0317 (6)	−0.0030 (6)	0.0066 (6)	−0.0054 (5)
C9	0.0460 (11)	0.0347 (10)	0.0453 (11)	−0.0019 (9)	0.0049 (9)	−0.0112 (9)
O10	0.0441 (8)	0.0368 (7)	0.0524 (8)	−0.0069 (6)	0.0084 (7)	−0.0168 (6)
C11	0.0559 (14)	0.0432 (12)	0.0881 (19)	0.0039 (11)	0.0269 (13)	−0.0142 (12)
C12	0.099 (2)	0.0689 (15)	0.0468 (13)	0.0017 (18)	−0.0115 (15)	−0.0215 (12)
O13	0.0267 (6)	0.0445 (7)	0.0323 (6)	−0.0030 (7)	−0.0031 (5)	0.0103 (5)
C14	0.0252 (9)	0.0569 (12)	0.0360 (10)	−0.0085 (9)	−0.0049 (8)	0.0145 (9)
O15	0.0268 (6)	0.0635 (9)	0.0400 (7)	−0.0028 (6)	−0.0055 (6)	0.0040 (7)
C16	0.0345 (9)	0.0272 (9)	0.0399 (11)	−0.0008 (8)	−0.0039 (8)	−0.0005 (8)
C17	0.0400 (11)	0.0813 (16)	0.0433 (12)	0.0001 (12)	0.0055 (9)	−0.0016 (11)
C18	0.0451 (13)	0.0847 (18)	0.0752 (17)	−0.0270 (13)	−0.0131 (12)	0.0452 (15)

Geometric parameters (Å, º) top

C1—C2	1.530 (2)	C9—C12	1.511 (3)
C1—O5	1.419 (2)	C11—H111	0.980
C1—O13	1.418 (2)	C11—H112	0.965
C1—C16	1.514 (2)	C11—H113	0.973
C2—C3	1.535 (2)	C12—H121	0.977
C2—O10	1.427 (2)	C12—H122	0.966
C2—H21	0.991	C12—H123	0.977
C3—C4	1.514 (2)	O13—C14	1.448 (2)
C3—O8	1.433 (2)	C14—O15	1.431 (2)
C3—H31	0.989	C14—C17	1.506 (3)
C4—O5	1.446 (2)	C14—C18	1.510 (3)
C4—C6	1.521 (2)	O15—C16	1.423 (2)
C4—H41	0.993	C16—H161	0.979
C6—O7	1.413 (2)	C16—H162	1.005
C6—H61	0.997	C17—H171	0.975
C6—H62	0.992	C17—H172	0.986
O7—H1	0.841	C17—H173	0.978
O8—C9	1.428 (2)	C18—H181	0.958
C9—O10	1.424 (2)	C18—H182	0.960
C9—C11	1.516 (3)	C18—H183	0.973

C2—C1—O5	105.60 (14)	C2—O10—C9	108.83 (14)
C2—C1—O13	110.00 (14)	C9—C11—H111	107.8
O5—C1—O13	111.31 (13)	C9—C11—H112	108.3
C2—C1—C16	117.33 (13)	H111—C11—H112	110.5
O5—C1—C16	109.94 (15)	C9—C11—H113	108.0
O13—C1—C16	102.76 (14)	H111—C11—H113	112.1
C1—C2—C3	105.37 (14)	H112—C11—H113	110.1
C1—C2—O10	109.14 (15)	C9—C12—H121	107.6
C3—C2—O10	105.08 (14)	C9—C12—H122	109.0
C1—C2—H21	111.1	H121—C12—H122	109.9
C3—C2—H21	113.8	C9—C12—H123	108.3
O10—C2—H21	111.9	H121—C12—H123	111.9
C2—C3—C4	104.93 (14)	H122—C12—H123	110.0
C2—C3—O8	103.91 (14)	C1—O13—C14	108.60 (14)
C4—C3—O8	109.08 (14)	O13—C14—O15	105.56 (15)
C2—C3—H31	112.4	O13—C14—C17	110.45 (17)
C4—C3—H31	114.6	O15—C14—C17	107.98 (17)
O8—C3—H31	111.2	O13—C14—C18	107.55 (17)
C3—C4—O5	105.01 (13)	O15—C14—C18	111.19 (18)
C3—C4—C6	112.58 (15)	C17—C14—C18	113.81 (19)
O5—C4—C6	111.65 (14)	C14—O15—C16	108.83 (13)
C3—C4—H41	110.7	C1—C16—O15	103.25 (14)
O5—C4—H41	107.5	C1—C16—H161	109.8
C6—C4—H41	109.2	O15—C16—H161	109.8
C4—O5—C1	109.09 (13)	C1—C16—H162	111.8
C4—C6—O7	112.30 (15)	O15—C16—H162	109.3
C4—C6—H61	107.7	H161—C16—H162	112.5
O7—C6—H61	108.3	C14—C17—H171	107.2
C4—C6—H62	107.4	C14—C17—H172	108.5
O7—C6—H62	110.4	H171—C17—H172	108.4
H61—C6—H62	110.6	C14—C17—H173	109.3
C6—O7—H1	109.2	H171—C17—H173	112.4
C3—O8—C9	108.05 (14)	H172—C17—H173	111.0
O8—C9—O10	104.52 (15)	C14—C18—H181	108.9
O8—C9—C11	110.51 (17)	C14—C18—H182	108.8
O10—C9—C11	110.24 (17)	H181—C18—H182	109.5
O8—C9—C12	107.93 (17)	C14—C18—H183	109.2
O10—C9—C12	109.1 (2)	H181—C18—H183	109.2
C11—C9—C12	114.1 (2)	H182—C18—H183	111.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O8ⁱ	0.84	2.19	2.962 (2)	152

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Acknowledgements

Financial support provided by the Xunta de Galicia (RS) is gratefully acknowledged.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, C. K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Bols, M. (1996). Carbohydrate Building Blocks. New York: John Wiley & Sons, Inc. Google Scholar
Cree, G. M. & Perlin, A. S. (1968). Can. J. Biochem. 46, 765–770. CrossRef CAS PubMed Web of Science Google Scholar
Granstrom, T. B., Takata, G., Tokuda, M. & Izumori, K. (2004). J. Biosci. Bioeng. 97, 89–94. Web of Science CrossRef PubMed Google Scholar
Itoh, H. & Izumori, K. (1996). J. Ferment. Bioeng. 81, 351–353. CrossRef CAS Web of Science Google Scholar
Itoh, H., Sato, I. & Izumori, K. (1995). J. Ferment. Bioeng. 80, 101–103. CrossRef CAS Web of Science Google Scholar
Izumori, K. (2002). Naturwissenschaften, 89, 120-124. Web of Science CrossRef PubMed CAS Google Scholar
James, K. J., Tatchell, A. R. & Ray, P. R. (1967). J. Chem. Soc. C, pp. 2681–2686. Google Scholar
Joseph, C. C., Regeling, H., Zwanenburg, B. & Chittenden, G. J. F. (2002). Carbohydr. Res. 337, 1083–1087. Web of Science CrossRef PubMed CAS Google Scholar
Lichtenthaler, F. W. & Peters, S. (2004). C. R. Chim. 7, 65–90. Web of Science CrossRef CAS Google Scholar
Nonius (1997-2001). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Prisbe, E. J., Smejkal, J., Verdehyden, J. P. H. & Moffat, J. G. (1976). J. Org. Chem. 41, 1836–1846. CrossRef PubMed CAS Web of Science Google Scholar
Soengas, R., Izumori, K., Simone, M. I., Watkin, D. J., Skytte, U. P., Soetaert, W. & Fleet, G. W. J. (2005). Tetrahedron Lett. 46, 5755–5759. Web of Science CrossRef CAS Google Scholar
Soengas, R., Wormald, M. R., Dwek, R. A., Izumori, K., Watkin, D. J., Skytte, U. P. & Fleet, G. W. J. (2005). In preparation. Google Scholar
Steiger, M. & Reichstein, T. (1935). Helv. Chim. Acta, 18, 790–799. CrossRef CAS Google Scholar
Steiger, M. & Reichstein, T. (1936). Helv. Chim. Acta, 19, 184–189. CrossRef CAS Google Scholar
Sun, Y., Hayakawa, S. & Izumori, K. (2004). J. Agric. Food. Chem. 52, 1293–1299. Web of Science CrossRef PubMed CAS Google Scholar
Sun, Y., Hayakawa, S., Puangmanee, S. & Izumori, K. (2005). Food Chem. In the press (doi 10.1016/j.foodchem. 2005.01.033). Google Scholar
Takeshita, K., Suga, A., Takada, G. & Izumori, K. (2000). J. Biosci. Bioeng. 90, 453–455. Web of Science CrossRef PubMed CAS Google Scholar
Tipson, S., Brady, R. & West, B. (1971). Carbohydr. Res. 16, 383–393. CrossRef CAS Web of Science Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar

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