2,2′:5,6-Di-O-iso­propyl­idene-2-C-hydro­xymethyl-d-talono-1,4-lactone

Harding, C.C.; Watkin, D.J.; Cowley, A.R.; Soengas, R.; Skytte, U.P.; Fleet, G.W.J.

doi:10.1107/S1600536804033549

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 2| February 2005| Pages o250-o252

https://doi.org/10.1107/S1600536804033549

2,2′:5,6-Di-O-isopropylidene-2-C-hydroxymethyl-D-talono-1,4-lactone

Christopher C. Harding,^a ^* David J. Watkin,^a Andrew R. Cowley,^a Raquel Soengas,^b Ulla P. Skytte ^c 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, and ^cArla Foods Ingredients, Viby J, Denmark
^*Correspondence e-mail: christopher.harding@seh.ox.ac.uk

(Received 10 December 2004; accepted 17 December 2004; online 8 January 2005)

A second crystalline diacetonide, the title compound, C₁₃H₂₀O₇, has been isolated from the sequential treatment of D-tagatose with aqueous sodium cyanide, followed by acetone in the presence of acid. Structural ambiguities with regard to the size of both the lactone and ketal rings are resolved by the X-ray crystallographic analysis.

Comment

Although the branched carbon-chain lactones formed by the Kiliani extension of ketoses are not readily separated, treatment of the crude product mixture forms a series of diacetonides, from which the major products can be separated (Hotchkiss et al., 2004 ) and their structures determined by X-ray crystallographic analysis (Cowley et al., 2004 ; van Ameijde et al., 2004 ). Such materials have considerable potential as a new class of readily available chiral building blocks and bioactive scaffolds (Lichtenthaler & Peters, 2004 ; Bols, 1996 ). Developments in biotechnology are leading to the ready availability of almost any ketohexose or ketopentose by a combination of microbial oxidation and enzyme-catalysed epimerizations (Granstrom et al., 2004 ). In particular, D-tagatose, (1), hitherto considered a rare sugar, is a healthy sweetener prepared cheaply from whey, and used in soft drinks and ready-to-eat cereals (Skytte, 2002 ).

The sequential treatment of D-tagatose, (1), with sodium cyanide, followed by extraction of the crude lactones with acetone in the presence of sulfuric acid, gave a mixture of diacetonides; the cis-fused diacetonide (2) was easily crystallized as one of two major products (Shallard-Brown et al., 2004 ). Further purification allowed the crystallization of a second diacetonide; NMR and other spectroscopic studies on this material left considerable ambiguity with regard to the ring sizes of both the acetonides and the lactone. X-ray crystallographic analysis firmly established the structure as the acetonide, (3), in which there is a spiro-acetonide. It is anticipated that both the diacetonides, (2) and (3), will rapidly be established as ideal starting materials for a range of complex bioactive products.

Figure 1
The title molecule at 120 K, with displacement ellipsoids drawn at the 50% probability level. Note the fairly large displacement parameters on fragment C6/C9/C10, suggesting some minor disorder of atoms in this part of the molecule.

Figure 2
Packing diagram of the title molecule, viewed along the a axis. The molecules form independent hydrogen-bonded ribbons (dashed lines) parallel to a.

Figure 3
View of a section of one hydrogen-bonded ribbon (dashed lines), viewed along c.

Experimental

The title material was crystallized from diethyl ether by inward diffusion of n-hexane, to yield very fragile plate-like colourless crystals. The full experimental method is currently being prepared for publication.

Crystal data

C₁₃H₂₀O₇
M_r = 288.30
Orthorhombic, P2₁2₁2₁
a = 5.8303 (1) Å
b = 9.8983 (2) Å
c = 24.1599 (4) Å
V = 1394.27 (4) Å³
Z = 4
D_x = 1.373 Mg m⁻³
Mo Kα radiation
Cell parameters from 2281 reflections
θ = 5–30°
μ = 0.11 mm⁻¹
T = 120 K
Plate, colourless
0.30 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997 ) T_min = 0.99, T_max = 0.99
3990 measured reflections
2337 independent reflections
2033 reflections with I > 2.00 u(I)
R_int = 0.012
θ_max = 30.0°
h = −8 → 8
k = −13 → 13
l = −33 → 34

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.078
S = 0.96
2337 reflections
261 parameters
All H-atom parameters refined
w = 1/[σ²(F²) + 0.04 + 0.32P] where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max = 0.001
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O14—H18⋯O15ⁱ	0.823 (15)	1.977 (16)	2.7947 (15)	172 (2)
Symmetry code: (i) $[{\script{1\over 2}}+x,{\script{1\over 2}}-y,1-z]$ .

All H atoms were observed in a difference electron-density map. The hydroxyl H atom was placed as found and the others were positioned geometrically (C—H = 1.00 Å). All were refined with slack restraints [distance s.u. values of 0.02 Å and angle s.u. values of 2.0°; U_iso(H) = 1.2U_eq(parent), s.u. = 0.02 Å²]. In the absence of significant anomalous scattering effects, Friedel pairs were merged. The absolute configuration is known from the synthesis.

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 3, global. DOI: https://doi.org/10.1107/S1600536804033549/rz6034sup1.cif

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S1600536804033549/rz60343sup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1997); 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.

2,2':5,6-Di-O-isopropylidene-2-C-hydroxmethyl-D-talono-1,4-lactone top

Crystal data top

C₁₃H₂₀O₇	D_x = 1.373 Mg m⁻³
M_r = 288.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 2281 reflections
a = 5.8303 (1) Å	θ = 5–30°
b = 9.8983 (2) Å	µ = 0.11 mm⁻¹
c = 24.1599 (4) Å	T = 120 K
V = 1394.27 (4) Å³	Plate, colourless
Z = 4	0.30 × 0.10 × 0.05 mm
F(000) = 616

Data collection top

Nonius KappaCCD diffractometer	2033 reflections with I > 2.00u(I)
Graphite monochromator	R_int = 0.012
ω scans	θ_max = 30.0°, θ_min = 5.3°
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)	h = −8→8
T_min = 0.99, T_max = 0.99	k = −13→13
3990 measured reflections	l = −33→34
2337 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 not defined
wR(F²) = 0.078	w = 1/[σ²(F²) + 0.04 + 0.32P] where P = [max(F_o²,0) + 2F_c²]/3
S = 0.96	(Δ/σ)_max = 0.001
2337 reflections	Δρ_max = 0.27 e Å⁻³
261 parameters	Δρ_min = −0.22 e Å⁻³
83 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.1689 (3)	0.01089 (13)	0.52121 (6)	0.0168
C2	0.2950 (3)	0.07139 (14)	0.47152 (6)	0.0180
C3	0.3181 (3)	−0.05664 (14)	0.43610 (6)	0.0181
C4	0.3765 (3)	−0.03576 (15)	0.37596 (6)	0.0231
O5	0.2247 (3)	0.05865 (10)	0.35061 (4)	0.0281
C6	0.1814 (3)	0.01631 (16)	0.29466 (6)	0.0238
O7	0.3191 (2)	−0.10136 (12)	0.28587 (4)	0.0278
C8	0.3557 (4)	−0.16024 (16)	0.33913 (6)	0.0266
C9	0.2589 (4)	0.12464 (19)	0.25547 (7)	0.0367
C10	−0.0687 (4)	−0.0186 (3)	0.28992 (11)	0.0487
O11	0.09362 (19)	−0.12025 (11)	0.44206 (4)	0.0191
C12	0.0067 (3)	−0.08815 (14)	0.49236 (6)	0.0182
O13	−0.1707 (2)	−0.13485 (11)	0.50882 (5)	0.0249
O14	0.5078 (2)	0.12981 (11)	0.48428 (5)	0.0261
O15	0.0460 (2)	0.10481 (10)	0.55412 (4)	0.0198
C16	0.1035 (3)	0.08323 (15)	0.61233 (6)	0.0197
O17	0.2065 (2)	−0.04655 (10)	0.61372 (4)	0.0200
C18	0.3270 (3)	−0.06166 (15)	0.56271 (6)	0.0200
C19	0.2683 (4)	0.19259 (17)	0.63039 (8)	0.0311
C20	−0.1146 (3)	0.0792 (2)	0.64570 (7)	0.0307
H21	0.200 (3)	0.1372 (15)	0.4519 (6)	0.0244 (18)*
H31	0.433 (3)	−0.1159 (16)	0.4525 (6)	0.0252 (18)*
H41	0.537 (3)	−0.0016 (16)	0.3746 (6)	0.0322 (19)*
H81	0.228 (3)	−0.2165 (17)	0.3499 (7)	0.0352 (19)*
H82	0.495 (3)	−0.2165 (17)	0.3399 (7)	0.0371 (19)*
H91	0.232 (4)	0.094 (2)	0.2183 (7)	0.0642 (19)*
H92	0.169 (4)	0.2046 (18)	0.2630 (8)	0.0645 (19)*
H93	0.424 (3)	0.141 (2)	0.2611 (8)	0.0645 (19)*
H101	−0.101 (4)	−0.048 (2)	0.2525 (7)	0.0857 (19)*
H102	−0.157 (4)	0.0607 (19)	0.2965 (10)	0.0849 (19)*
H103	−0.116 (4)	−0.089 (2)	0.3153 (9)	0.0860 (19)*
H181	0.342 (3)	−0.1574 (14)	0.5542 (6)	0.0283 (18)*
H182	0.475 (3)	−0.0195 (16)	0.5634 (6)	0.0265 (18)*
H191	0.311 (3)	0.1772 (19)	0.6686 (7)	0.0546 (19)*
H192	0.196 (3)	0.2799 (16)	0.6274 (8)	0.0538 (19)*
H193	0.407 (3)	0.191 (2)	0.6072 (8)	0.0550 (19)*
H201	−0.075 (3)	0.0641 (19)	0.6844 (7)	0.0531 (19)*
H202	−0.213 (3)	0.0038 (18)	0.6322 (8)	0.0532 (19)*
H203	−0.193 (3)	0.1664 (17)	0.6419 (8)	0.0533 (19)*
H18	0.509 (4)	0.2061 (17)	0.4707 (9)	0.0471 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0214 (7)	0.0135 (6)	0.0156 (6)	0.0019 (6)	0.0006 (6)	−0.0003 (5)
C2	0.0237 (7)	0.0144 (6)	0.0160 (6)	−0.0014 (6)	−0.0017 (6)	0.0012 (5)
C3	0.0209 (7)	0.0157 (6)	0.0176 (6)	−0.0019 (6)	0.0014 (6)	0.0005 (5)
C4	0.0331 (9)	0.0179 (7)	0.0184 (7)	0.0003 (7)	0.0049 (7)	0.0009 (6)
O5	0.0520 (8)	0.0181 (5)	0.0141 (5)	0.0081 (6)	0.0012 (5)	−0.0004 (4)
C6	0.0321 (9)	0.0217 (7)	0.0175 (7)	0.0007 (7)	0.0027 (7)	−0.0057 (6)
O7	0.0420 (7)	0.0240 (5)	0.0175 (5)	0.0070 (6)	0.0060 (5)	−0.0030 (4)
C8	0.0401 (10)	0.0211 (7)	0.0185 (7)	0.0042 (8)	0.0044 (7)	−0.0009 (6)
C9	0.0634 (14)	0.0295 (8)	0.0172 (7)	0.0065 (10)	0.0052 (9)	0.0019 (6)
C10	0.0353 (10)	0.0465 (12)	0.0642 (14)	0.0012 (10)	0.0024 (11)	−0.0275 (11)
O11	0.0224 (5)	0.0172 (5)	0.0178 (5)	−0.0032 (5)	0.0013 (5)	−0.0018 (4)
C12	0.0222 (7)	0.0133 (6)	0.0192 (7)	0.0016 (6)	0.0002 (6)	0.0008 (5)
O13	0.0238 (5)	0.0203 (5)	0.0306 (6)	−0.0022 (5)	0.0056 (5)	−0.0022 (4)
O14	0.0286 (6)	0.0197 (5)	0.0300 (6)	−0.0090 (5)	−0.0042 (5)	0.0038 (5)
O15	0.0276 (5)	0.0165 (5)	0.0154 (5)	0.0068 (5)	−0.0019 (5)	−0.0016 (4)
C16	0.0233 (7)	0.0202 (7)	0.0156 (6)	0.0051 (7)	−0.0022 (6)	−0.0015 (5)
O17	0.0272 (6)	0.0181 (5)	0.0146 (5)	0.0054 (5)	0.0018 (5)	0.0014 (4)
C18	0.0257 (7)	0.0188 (6)	0.0156 (6)	0.0059 (7)	0.0009 (6)	0.0005 (5)
C19	0.0359 (10)	0.0214 (7)	0.0358 (9)	0.0021 (8)	−0.0144 (8)	−0.0034 (7)
C20	0.0294 (9)	0.0410 (9)	0.0218 (8)	0.0095 (9)	0.0041 (7)	0.0010 (7)

Geometric parameters (Å, º) top

C1—C2	1.530 (2)	C9—H92	0.968 (16)
C1—C12	1.530 (2)	C9—H93	0.985 (16)
C1—O15	1.4179 (17)	C10—H101	0.969 (17)
C1—C18	1.539 (2)	C10—H102	0.953 (17)
C2—C3	1.535 (2)	C10—H103	0.967 (17)
C2—O14	1.4030 (19)	O11—C12	1.3545 (18)
C2—H21	0.978 (14)	C12—O13	1.2003 (19)
C3—C4	1.507 (2)	O14—H18	0.823 (15)
C3—O11	1.4593 (18)	O15—C16	1.4614 (17)
C3—H31	0.975 (14)	C16—O17	1.4183 (18)
C4—O5	1.425 (2)	C16—C19	1.512 (2)
C4—C8	1.525 (2)	C16—C20	1.506 (2)
C4—H41	0.998 (15)	O17—C18	1.4265 (18)
O5—C6	1.4376 (18)	C18—H181	0.974 (14)
C6—O7	1.431 (2)	C18—H182	0.960 (14)
C6—C9	1.500 (2)	C19—H191	0.967 (16)
C6—C10	1.503 (3)	C19—H192	0.963 (15)
O7—C8	1.4288 (19)	C19—H193	0.984 (16)
C8—H81	0.965 (15)	C20—H201	0.975 (15)
C8—H82	0.987 (15)	C20—H202	0.997 (16)
C9—H91	0.963 (16)	C20—H203	0.981 (16)

C2—C1—C12	100.99 (11)	C6—C9—H93	108.9 (12)
C2—C1—O15	115.24 (11)	H91—C9—H93	109.8 (14)
C12—C1—O15	111.28 (13)	H92—C9—H93	111.9 (14)
C2—C1—C18	113.96 (13)	C6—C10—H101	109.2 (13)
C12—C1—C18	111.58 (11)	C6—C10—H102	108.9 (13)
O15—C1—C18	104.07 (11)	H101—C10—H102	107.5 (15)
C1—C2—C3	98.99 (11)	C6—C10—H103	113.3 (13)
C1—C2—O14	114.45 (12)	H101—C10—H103	108.7 (15)
C3—C2—O14	112.67 (13)	H102—C10—H103	109.2 (15)
C1—C2—H21	111.5 (9)	C3—O11—C12	108.84 (11)
C3—C2—H21	109.3 (9)	C1—C12—O11	109.11 (12)
O14—C2—H21	109.5 (9)	C1—C12—O13	128.93 (14)
C2—C3—C4	116.37 (12)	O11—C12—O13	121.96 (14)
C2—C3—O11	102.87 (12)	C2—O14—H18	107.5 (18)
C4—C3—O11	110.93 (12)	C1—O15—C16	109.14 (10)
C2—C3—H31	109.3 (9)	O15—C16—O17	104.61 (11)
C4—C3—H31	108.6 (9)	O15—C16—C19	108.60 (13)
O11—C3—H31	108.5 (9)	O17—C16—C19	111.89 (13)
C3—C4—O5	111.35 (13)	O15—C16—C20	108.98 (13)
C3—C4—C8	115.71 (13)	O17—C16—C20	108.71 (13)
O5—C4—C8	103.27 (13)	C19—C16—C20	113.64 (14)
C3—C4—H41	107.0 (9)	C16—O17—C18	106.44 (11)
O5—C4—H41	110.3 (10)	C1—C18—O17	102.65 (12)
C8—C4—H41	109.2 (9)	C1—C18—H181	111.9 (10)
C4—O5—C6	108.79 (11)	O17—C18—H181	109.2 (9)
O5—C6—O7	106.16 (13)	C1—C18—H182	110.4 (9)
O5—C6—C9	109.39 (13)	O17—C18—H182	112.5 (9)
O7—C6—C9	108.60 (14)	H181—C18—H182	110.1 (12)
O5—C6—C10	108.02 (16)	C16—C19—H191	108.9 (11)
O7—C6—C10	110.25 (15)	C16—C19—H192	110.1 (11)
C9—C6—C10	114.11 (19)	H191—C19—H192	108.9 (13)
C6—O7—C8	106.38 (11)	C16—C19—H193	110.4 (11)
C4—C8—O7	102.00 (12)	H191—C19—H193	109.3 (13)
C4—C8—H81	111.7 (10)	H192—C19—H193	109.2 (13)
O7—C8—H81	111.3 (10)	C16—C20—H201	108.5 (12)
C4—C8—H82	112.2 (10)	C16—C20—H202	109.3 (11)
O7—C8—H82	111.7 (10)	H201—C20—H202	109.6 (13)
H81—C8—H82	107.8 (12)	C16—C20—H203	108.7 (11)
C6—C9—H91	108.2 (12)	H201—C20—H203	109.6 (13)
C6—C9—H92	107.6 (12)	H202—C20—H203	111.1 (13)
H91—C9—H92	110.4 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O14—H18···O15ⁱ	0.82 (2)	1.98 (2)	2.7947 (15)	172 (2)

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

Acknowledgements

Financial support (to RS) provided through the European Community's Human Potential Programme under contract HPRN-CT-2002-00173 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
Ameijde, J. van, Cowley, A. R., Fleet, G. W. J., Nash, R. J., Simone, M. I. & Soengas, R. (2004). Acta Cryst. E60, o2140–o2141. Web of Science CSD CrossRef IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Bols, M. (1996). Carbohydrate Building Blocks (ISBN 0-471-13339-6). New York: John Wiley & Sons. Google Scholar
Cowley, A. R., Fleet, G. W. J., Simone, M. I. & Soengas, R. (2004). Acta Cryst. E60, o2142–o2143. Web of Science CSD CrossRef IUCr Journals 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
Hotchkiss, D., Soengas, R., Simone, M. I., van Ameijde, J., Hunter, S., Cowley, A. R. & Fleet, G. W. J. (2004). Tetrahedron Lett. 45, 9461–9464. Web of Science CrossRef CAS Google Scholar
Lichtenthaler, F. W. & Peters, S. (2004) Compt. Rend. Chim. 7, 65–90. Web of Science CrossRef CAS Google Scholar
Nonius (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
Shallard-Brown, H. A., Harding, C. C., Watkin, D. J., Soengas, R., Skytte, U. P. & Fleet, G. W. J. (2004). Acta Cryst. E60, o2163–o2164. Web of Science CSD CrossRef IUCr Journals Google Scholar
Skytte, U. P. (2002). Cereal Foods World, 47, 224–227. Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

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