Tris[(6S)-6-hy­droxy-4-epi-shikimic acid] monohydrate: an enanti­omerically pure hy­droxy­lated shikimic acid derived from methyl shikimate

Griesbeck, A.G.; Miara, C.; Neudörfl, J.-M.

doi:10.1107/S1600536812041256

Volume 68
Part 11
Pages o3149-o3150
November 2012

Received 5 September 2012
Accepted 1 October 2012
Online 20 October 2012

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.008 Å
R = 0.054
wR = 0.102
Data-to-parameter ratio = 7.5
Details

Tris[(6S)-6-hydroxy-4-epi-shikimic acid] monohydrate: an enantiomerically pure hydroxylated shikimic acid derived from methyl shikimate

Axel G. Griesbeck,^a ^* Claus Miara ^a and Jörg-M. Neudörfl ^a

^aDepartment of Chemistry, University of Cologne, Greinstr. 4, 50939 Koeln, Germany
Correspondence e-mail: griesbeck@uni-koeln.de

The title compound, 3C₇H₁₀O₆·H₂O, is the enantiomerically pure product of a multi-step synthesis from the enantiomerically pure natural shikimic acid. The asymmetric unit contains three molecules of the acid and one molecule of water. The cyclohexene rings of the acids have half-chair conformations. The carboxylate, the four hydroxide groups and the additional water molecule form a complex three-dimensional hydrogen-bonding network.

Related literature

A series of antitumor-active marine natural carbasugars has been isolated in the last two decades with a cyclohexene-1-carboxylate core structure and four contiguous stereogenic centers (Numata et al., 1997). The relative configuration of these compounds, the pericosines, has been a matter of debate since the first reports on the isolation (Usami et al., 2008, 2009). By means of detailed NMR analysis of the natural compound pericosine D0 and comparison with the NMR data published for the 6-hydroxy-5-epishikimic acid described herein, the absolute and relative configuration was established (Usami et al., 2006, 2011). This reveals the importance of this X-ray crystallographic determination that finally proves the assignments that resulted from spectroscopic analyses. For the synthesis, see: Griesbeck et al. (2007).

Experimental

Crystal data

3C₇H₁₀O₆·H₂O
M_r = 588.47
Monoclinic, P 2₁
a = 11.2561 (17) Å
b = 7.7049 (11) Å
c = 13.9688 (14) Å
= 91.672 (8)°
V = 1211.0 (3) Å³
Z = 2
Mo K radiation
= 0.15 mm^-1
T = 100 K
0.20 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
5629 measured reflections
2786 independent reflections
1399 reflections with I > 2(I)
R_int = 0.085

Refinement

R[F² > 2(F²)] = 0.054
wR(F²) = 0.102
S = 0.88
2786 reflections
371 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.27 e Å^-3
_min = -0.28 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O2-H2O1Aⁱ	0.84	1.81	2.624 (5)	164
O3-H3O4Aⁱⁱ	0.84	1.90	2.705 (5)	161
O4-H4O6ⁱⁱⁱ	0.84	1.94	2.738 (6)	157
O5-H5O6B^iv	0.84	2.08	2.736 (5)	134
O6-H6O3ⁱⁱⁱ	0.84	1.89	2.718 (6)	169
O6A-H6AO3A^v	0.84	1.99	2.764 (6)	153
O4A-H4AO6A^v	0.84	1.88	2.712 (6)	168
O5B-H5BO5	0.84	1.93	2.765 (5)	171
O5A-H5AO3B	0.84	2.06	2.882 (5)	164
O2A-H2AO1^vi	0.84	1.84	2.664 (5)	167
O6B-H6BO1B^iv	0.84	2.05	2.801 (5)	149
O4B-H4BO4A	0.84	2.10	2.835 (6)	147
O2B-H2BO5B^vii	0.84	1.85	2.663 (6)	163
O3B-H3BO1W	0.84	1.88	2.703 (6)	166
O3A-H3AO4^iv	0.84	1.89	2.705 (5)	163
O1W-H1W1O5A^viii	0.85 (2)	1.95 (2)	2.794 (7)	173 (8)
O1W-H1W2O2B^ix	0.86 (2)	2.16 (5)	2.967 (6)	157 (11)
Symmetry codes: (i) $[-x, y-{\script{3\over 2}}, -z]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z-1]$ ; (iii) $[-x-1, y+{\script{1\over 2}}, -z-1]$ ; (iv) $[-x, y+{\script{1\over 2}}, -z-1]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (vi) $[-x, y+{\script{3\over 2}}, -z]$ ; (vii) x, y-1, z; (viii) $[-x, y-{\script{1\over 2}}, -z]$ ; (ix) $[-x, y+{\script{1\over 2}}, -z]$ .

Data collection: COLLECT (Hooft 1998); cell refinement: DENZO (Otwinowski & Minor 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SCHAKAL99 (Keller 1999); software used to prepare material for publication: PLATON (Spek 2009).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GG2099 ).

Acknowledgements

This research was supported by the Deutsche Forschungsgemeinschaft and by University start-up funding (2004-2005).

References

Griesbeck, A. G., Miara, C. & Neudörfl, J. (2007). Arkivoc, 8, 216-223.
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Keller, E. (1999). SCHAKAL99. University of Freiburg, Germany.
Numata, A., Iritani, M., Yamada, T., Minoura, K., Matsumura, E., Yamori, T. & Tsuruo, T. (1997). Tetrahedron Lett. 38, 8215-8218.
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.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.
Usami, Y., Horibe, Y., Takaoka, I., Ichikawa, H. & Arimoto, M. (2006). Synlett, 10, 1598-1600.
Usami, Y. & Mizuki, K. (2011). J. Nat. Prod. 74, 877-881.
Usami, Y., Mizuki, K., Ichikawa, H. & Arimoto, M. (2008). Tetrahedron Asymmetry, 19, 1461-1464.
Usami, Y., Ohsugi, M., Mizuki, K., Ichikawa, H. & Arimoto, M. (2009). Org. Lett. 11, 2699-2701.

organic compounds