Redetermination and absolute configuration of (+)-7-epiclusianone

Christian, O.E.; Fronczek, F.R.; Ky, K.; Pradhan, S.; Manandhar, A.; Richmond, C.

doi:10.1107/S1600536812043784

Volume 68
Part 11
Pages o3222-o3223
November 2012

Received 19 October 2012
Accepted 22 October 2012
Online 27 October 2012

Key indicators
Single-crystal X-ray study
T = 90 K
Mean (C-C) = 0.002 Å
R = 0.028
wR = 0.074
Data-to-parameter ratio = 15.0
Details

Redetermination and absolute configuration of (+)-7-epiclusianone

Omar E. Christian,^a ^* Frank R. Fronczek,^b Khoa Ky,^a Shreedu Pradhan,^a Anjela Manandhar ^a and Cecilia Richmond ^c

^aDepartment of Chemistry, McNeese State University, Lake Charles, LA 70609, USA,^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA, and ^cLouisiana Environmental Research Center, McNeese State University, Lake Charles, LA 70609, USA
Correspondence e-mail: ochristian@mcneese.edu

The absolute configuration of 3-benzoyl-4-hydroxy-6,6-dimethyl-1,5,7-tris(3-methylbut-2-enyl)bicyclo[3.3.1]non-3-ene-2,9-dione, C₃₃H₄₂O₄, isolated from Hypericum hypericoides, has been determined. The previous study [Xiao et al. (2007). J. Nat. Prod. 70, 1779-1782] gave only the established relative configuration. The three stereogenic centers are now established as 1R, 5R and 7S on the basis of the refinement of the Flack absolute structure parameter against Cu K [alpha] data and correspond to a specific rotation of [ [alpha] ]_D²⁰ = +66°. The enol-hydroxy group forms an intramolecular O-HO hydrogen bond to close an S(6) ring.

Related literature

For a review of polycyclic polyprenylated acylphloroglucinols, see: Ciochina & Grossman (2006). For background to Clusiaceae metabolites, see: Garnsey et al. (2011); Zhang et al. (2010); Christian et al. (2008); Wu et al. (2008). For relative-configuration structure determinatons, see: Santos et al. (1998); Xiao et al. (2007); Martins et al. (2009). For related structures, see: McCandlish et al. (1976); Fronczek et al. (2012). For optical rotation results for the title compound, see: Piccinelli et al. (2005) and for related compounds, see: Tanaka et al. (2004). For keto-enol tautomerism in related compounds, see: Martins et al. (2007). For absolute configuration based on resonant scattering from light atoms, see: Hooft et al. (2008)

Experimental

Crystal data

C₃₃H₄₂O₄
M_r = 502.67
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.6177 (4) Å
b = 12.4157 (6) Å
c = 26.8632 (13) Å
V = 2874.2 (2) Å³
Z = 4
Cu K radiation
= 0.59 mm^-1
T = 90 K
0.25 × 0.24 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD DUO diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) T_min = 0.824, T_max = 0.889
17192 measured reflections
5171 independent reflections
5131 reflections with I > 2(I)
R_int = 0.029

Refinement

R[F² > 2(F²)] = 0.028
wR(F²) = 0.074
S = 1.03
5171 reflections
345 parameters
H atoms treated by a mixture of independent and constrained refinement
_max = 0.22 e Å^-3
_min = -0.14 e Å^-3
Absolute structure: Flack (1983), 2200 Friedel pairs
Flack parameter: 0.04 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O2-H2OO4	1.014 (16)	1.477 (16)	2.4368 (12)	155.7 (15)

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6978 ).

Acknowledgements

Financial support provided by the Louisiana Environmental Research Center (LERC), Chenier Plain Sustainability Initiative Collaboration Award # 687217-10-006. Upgrade of the diffractometer was made possible by grant No. LEQSF(2011-12)-ENH-TR-01, administered by the Louisiana Board of Regents.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Christian, O. E., McLean, S., Reynolds, W. F. & Jacobs, H. (2008). Nat. Prod. Commun. 3, 1781-1786.
Ciochina, R. & Grossman, R. B. (2006). Chem. Rev. 106, 3963-3986.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.
Fronczek, F. R., Christian, O. & Crockett, S. (2012). ACA Annual Meeting, Boston, MA, USA. Abstract S-81.
Garnsey, M. R., Matous, J. A., Kwiek, J. J. & Coltart, D. M. (2011). Bioorg. Med. Chem. Lett. 21, 2406-2409.
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96-103.
Martins, F. T., Assis, D. M., dos Santos, M. H., Camps, I., Veloso, M. P., Juliano, M. A., Alves, L. C. & Doriguetto, A. C. (2009). Eur. J. Med. Chem. 44, 1230-1239.
Martins, F. T., Cruz, J. W. Jr, Derogis, B. M. C., dos Santos, M. H., Veloso, M. P., Ellena, J. & Doriguetto, A. C. (2007). J. Braz. Chem. Soc. 18, 1515-1523.
McCandlish, L. E., Hanson, J. C. & Stout, G. H. (1976). Acta Cryst. B32, 1793-1801.
Piccinelli, A. L., Cuesta-Rubio, O., Chica, M. B., Mahmood, N., Pagano, B., Pavone, M., Barone, V. & Rastrelli, L. (2005). Tetrahedron, 61, 8206-8211.
Santos, M. H., Speziali, N. L., Nagem, T. J. & Oliveira, T. T. (1998). Acta Cryst. C54, 1990-1992.
Sheldrick, G. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Tanaka, N., Takaishi, Y., Shikishima, Y., Nakanishi, Y., Bastow, K., Lee, K.-H., Honda, G., Ito, M., Takeda, Y., Kodzhimatov, O. K. & Ashurmetov, O. (2004). J. Nat. Prod. 67, 1870-1875.
Wu, C.-C., Yen, M.-Y., Yang, S.-C. & Lin, C.-N. (2008). J. Nat. Prod. 71, 1027-1031.
Xiao, Z. Y., Mu, Q., Shiu, W. K. P., Zeng, Y. H. & Gibbons, S. (2007). J. Nat. Prod. 70, 1779-1782.
Zhang, Q., Mitasev, B., Qi, J. & Proco, J. A. Jr (2010). J. Am. Chem. Soc. 132, 14212-14215.

organic compounds

Redetermination and absolute configuration of (+)-7-epiclusianone

Related literature

Experimental

Crystal data

Data collection

Refinement

Acknowledgements

References