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Volume 68 
Part 1 
Pages o41-o42  
January 2012  

Received 25 October 2011
Accepted 1 December 2011
Online 7 December 2011

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Key indicators
Single-crystal X-ray study
T = 298 K
Mean [sigma](C-C) = 0.005 Å
R = 0.047
wR = 0.118
Data-to-parameter ratio = 9.4
Details
Open access

Kallolide A acetate pyrazoline

Idaliz Rodríguez-Escudero,a* Jeffrey Marreroa and Abimael D. Rodrígueza

aPO Box 70377, University of Puerto Rico, San Juan, PR 00936-0377, Puerto Rico
Correspondence e-mail: idalizrodriguez@gmail.com

In the crystal structure of kallolide A acetate pyrazoline [systematic name: 7-methyl-16-oxo-4,10-bis(prop-1-en-2-yl)-17,18-dioxa-14,15-diazatetracyclo[9.4.2.16,9.01,12]octadeca-6,8,14-trien-5-yl acetate], C23H28N2O5, there is a 12-membered carbon macrocyclic structure. In addition, there is a trisubstituted furan ring, an approximately planar [gamma]-lactone ring [maximum deviation of 0.057 (3) Å] and a pyrazoline ring, the latter in an envelope conformation. The pyrazoline and the [gamma]-lactone rings are fused in a cis configuration. In the crystal, molecules are linked by weak C-H...O interactions, forming a two-dimensional network parallel to (001). An intramolecular C-H...O hydrogen bond is also present.

Related literature

For information on West Indies sea plumes, see: Bayer (1961[Bayer, F. M. (1961). The Shallow-Water Octocorallia of the West Indian Region. The Hague: Martinus Nijhof.]); Lasker & Coffroth (1983[Lasker, H. R. & Coffroth, M. A. (1983). Mar. Ecol. Prog. Ser. 13, 21-28.]); Humman (1996[Humman, P. (1996). Reef Coral Identification, edited by N. Deloach, pp. 50-53. Jacksonville: New World Publications.]); Sánchez et al. (1998[Sánchez, J. A., Zea, S. & Díaz, J. M. (1998). Caribb. J. Sci. 34, 250-264.]); Williams & Vennam (2001[Williams, G. C. & Vennam, J. S. (2001). Bull. Biol. Soc. Wash. 10, 71-95.]). For complete background to the natural product chemistry of the Gorgonian genus Pseudopterogorgia, see: Marrero et al. (2010[Marrero, J., Rodríguez, I. I. & Rodríguez, A. D. (2010). Comprehensive Natural Products II, Chemistry and Biology, vol. 2, pp. 363-429.]). For species of Pseudopterogorgia, see: Yoshioka (1997[Yoshioka, P. M. (1997). J. Exp. Mar. Biol. Ecol. 214, 167-178.]); Sánchez et al. (2003[Sánchez, J. A., McFadden, C. S., France, S. C. & Lasker, H. R. (2003). Mar. Biol. 142, 975-987.]); Sánchez & Lasker (2003[Sánchez, J. A. & Lasker, H. R. (2003). Proc. R. Soc. Lond. B, 270, 2039-2044.]). For the biological activity of diterpenoids from Pseudopterogorgia, see: Heckrodt & Mulzer (2005[Heckrodt, T. J. & Mulzer, J. (2005). Top. Curr. Chem. 244, 1-41.]). For more information on the pseudoterane-type of diterpenes, see: Bundurraga & Fenical (1982[Bundurraga, M. M. & Fenical, W. (1982). J. Am. Chem. Soc. 104, 6463-6465.]); Look et al. (1985[Look, S. A., Burch, M. T., Fenical, W., Qi-tai, Z. & Clardy, J. (1985). J. Org. Chem. 50, 5741-5746.]); Williams et al. (1987b[Williams, D., Andersen, R. J., van Duyne, G. D. & Clardy, J. (1987b). J. Org. Chem. 52, 332-335.]); Rodríguez & Soto (1996[Rodríguez, A. D. & Soto, J. J. (1996). Chem. Pharm. Bull. 44, 91-94.]); Marrero et al. (2006[Marrero, J., Ospina, C. A., Rodríguez, A. D., Baran, P., Zhao, H., Franzblau, S. G. & Ortega-Barria, E. (2006). Tetrahedron, 62, 6998-7008.]). For bioactive diterpenes isolated from Pseudopterogorgia kallos, see: Marrero et al. (2003a[Marrero, J., Rodríguez, A. D., Baran, P. & Raptis, R. G. (2003a). J. Org. Chem. 68, 4977-4979.],b[Marrero, J., Rodríguez, A. D., Baran, P. & Raptis, R. G. (2003b). Org. Lett. 5, 2551-2554.], 2004a[Marrero, J., Rodríguez, A. D., Baran, P. & Raptis, R. G. (2004a). Eur. J. Org. Chem. pp. 3909-3912.],b[Marrero, J., Rodríguez, A. D., Baran, P., Raptis, R. G., Sánchez, J. A., Ortega-Barria, E. & Capson, T. L. (2004b). Org. Lett. 6, 1661-1664.], 2005[Marrero, J., Rodríguez, A. D. & Barnes, C. L. (2005). Org. Lett. 7, 1877-1880.]). For biosynthetic relationship studies between cembrane- and pseudopterane-type diterpenes, see: Rodríguez & Shi (1998[Rodríguez, A. D. & Shi, J.-G. (1998). J. Org. Chem. 63, 420-421.]); Yang et al. (2010[Yang, Z., Li, Y. & Pattenden, G. (2010). Tetrahedron, 66, 6546-6549.]); Li & Pattenden (2011[Li, Y. & Pattenden, G. (2011). Tetrahedron Lett. 52, 31150-3319.]). For information on gersolane-type diterpenes and biosynthetic relationship studies between cembrane- and gersolane-type diterpenes, see: Williams et al. (1987a[Williams, D., Andersen, R. J., Parkanyi, L. & Clardy, J. (1987a). Tetrahedron Lett. 28, 5079-5080.]); Rodríguez et al. (1998[Rodríguez, A. D., Shi, J.-G. & Huang, S. D. (1998). J. Org. Chem. 63, 4425-4432.]). For complete background to the chemistry of furanocembranoids, pseudopteranes, gersolanes and related compounds, see: Roethle & Trauner (2008[Roethle, P. A. & Trauner, D. (2008). Nat. Prod. Rep. 25, 298-317.]). For the synthesis of kallolide A and kallolide A acetate, see: Marshall & Liao (1998[Marshall, J. A. & Liao, J. (1998). J. Org. Chem. 63, 5962-5970.]).

[Scheme 1]

Experimental

Crystal data

  • C23H28N2O5

  • Mr = 412.47

  • Orthorhombic, P 21 21 21

  • a = 10.593 (6) Å

  • b = 12.426 (7) Å

  • c = 17.099 (10) Å

  • V = 2251 (2) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.09 mm-1

  • T = 298 K

  • 0.40 × 0.30 × 0.10 mm
Data collection

  • Bruker SMART 1K CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a[Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.]) Tmin = 0.966, Tmax = 0.992

  • 14038 measured reflections

  • 2583 independent reflections

  • 2160 reflections with I > 2[sigma](I)

  • Rint = 0.041
Refinement

  • R[F2 > 2[sigma](F2)] = 0.047

  • wR(F2) = 0.118

  • S = 1.13

  • 2583 reflections

  • 276 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.35 e Å-3

  • [Delta][rho]min = -0.23 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
C8-H8...O5i 0.98 2.37 3.281 (4) 154
C9-H9...O4ii 0.98 2.52 3.319 (4) 139
C16-H16A...O5 0.96 2.54 3.347 (5) 142
Symmetry codes: (i) x+1, y, z; (ii) [-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART-NT (Bruker, 1998[Bruker (1998). SMART-NT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2456 ).

Acknowledgements

Support for this research was kindly provided by the NIH-MBRS Program and the DEGI at the University of Puerto Rico. The authors thank Dr Raphael G. Raptis for the use of the X-ray facilities and Dr Hong Zhao for her help with the data collection and initial structure refinement.

References

Bayer, F. M. (1961). The Shallow-Water Octocorallia of the West Indian Region. The Hague: Martinus Nijhof.
Bruker (1998). SMART-NT. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Bundurraga, M. M. & Fenical, W. (1982). J. Am. Chem. Soc. 104, 6463-6465.
Heckrodt, T. J. & Mulzer, J. (2005). Top. Curr. Chem. 244, 1-41.  [ChemPort]
Humman, P. (1996). Reef Coral Identification, edited by N. Deloach, pp. 50-53. Jacksonville: New World Publications.
Lasker, H. R. & Coffroth, M. A. (1983). Mar. Ecol. Prog. Ser. 13, 21-28.  [CrossRef]
Li, Y. & Pattenden, G. (2011). Tetrahedron Lett. 52, 31150-3319.
Look, S. A., Burch, M. T., Fenical, W., Qi-tai, Z. & Clardy, J. (1985). J. Org. Chem. 50, 5741-5746.  [CrossRef] [ChemPort]
Marrero, J., Ospina, C. A., Rodríguez, A. D., Baran, P., Zhao, H., Franzblau, S. G. & Ortega-Barria, E. (2006). Tetrahedron, 62, 6998-7008.  [ISI] [CrossRef] [ChemPort]
Marrero, J., Rodríguez, A. D., Baran, P. & Raptis, R. G. (2003a). J. Org. Chem. 68, 4977-4979.  [CSD] [CrossRef] [PubMed] [ChemPort]
Marrero, J., Rodríguez, A. D., Baran, P. & Raptis, R. G. (2003b). Org. Lett. 5, 2551-2554.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Marrero, J., Rodríguez, A. D., Baran, P. & Raptis, R. G. (2004a). Eur. J. Org. Chem. pp. 3909-3912.  [CSD] [CrossRef]
Marrero, J., Rodríguez, A. D., Baran, P., Raptis, R. G., Sánchez, J. A., Ortega-Barria, E. & Capson, T. L. (2004b). Org. Lett. 6, 1661-1664.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Marrero, J., Rodríguez, A. D. & Barnes, C. L. (2005). Org. Lett. 7, 1877-1880.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Marrero, J., Rodríguez, I. I. & Rodríguez, A. D. (2010). Comprehensive Natural Products II, Chemistry and Biology, vol. 2, pp. 363-429.
Marshall, J. A. & Liao, J. (1998). J. Org. Chem. 63, 5962-5970.  [CrossRef] [PubMed] [ChemPort]
Rodríguez, A. D. & Shi, J.-G. (1998). J. Org. Chem. 63, 420-421.  [PubMed]
Rodríguez, A. D., Shi, J.-G. & Huang, S. D. (1998). J. Org. Chem. 63, 4425-4432.
Rodríguez, A. D. & Soto, J. J. (1996). Chem. Pharm. Bull. 44, 91-94.  [PubMed]
Roethle, P. A. & Trauner, D. (2008). Nat. Prod. Rep. 25, 298-317.  [CrossRef] [PubMed] [ChemPort]
Sánchez, J. A. & Lasker, H. R. (2003). Proc. R. Soc. Lond. B, 270, 2039-2044.
Sánchez, J. A., McFadden, C. S., France, S. C. & Lasker, H. R. (2003). Mar. Biol. 142, 975-987.
Sánchez, J. A., Zea, S. & Díaz, J. M. (1998). Caribb. J. Sci. 34, 250-264.
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Williams, D., Andersen, R. J., Parkanyi, L. & Clardy, J. (1987a). Tetrahedron Lett. 28, 5079-5080.  [CrossRef] [ChemPort] [ISI]
Williams, D., Andersen, R. J., van Duyne, G. D. & Clardy, J. (1987b). J. Org. Chem. 52, 332-335.  [CrossRef] [ChemPort]
Williams, G. C. & Vennam, J. S. (2001). Bull. Biol. Soc. Wash. 10, 71-95.
Yang, Z., Li, Y. & Pattenden, G. (2010). Tetrahedron, 66, 6546-6549.  [ISI] [CrossRef] [ChemPort]
Yoshioka, P. M. (1997). J. Exp. Mar. Biol. Ecol. 214, 167-178.  [CrossRef] [ISI]

Acta Cryst (2012). E68, o41-o42   [ doi:10.1107/S1600536811051890 ]

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