(1S,2E,6R,7aR)-2-Benzyl­idene-1,6-dihy­droxy-2,3,5,6,7,7a-hexa­hydro-1H-pyrrolizin-3-one

Oliveira, F.L.; Freire, K.R.L.; Aparicio, R.; Coelho, F.

doi:10.1107/S1600536812018223

Volume 68
Part 5
Page o1572
May 2012

Received 17 March 2012
Accepted 23 April 2012
Online 28 April 2012

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R = 0.037
wR = 0.098
Data-to-parameter ratio = 13.4
Details

(1S,2E,6R,7aR)-2-Benzylidene-1,6-dihydroxy-2,3,5,6,7,7a-hexahydro-1H-pyrrolizin-3-one

F. L. Oliveira,^a K. R. L. Freire,^b R. Aparicio ^a ^* and F. Coelho ^b

^aLaboratory of Structural Biology and Crystallography, Institute of Chemistry, University of Campinas, CP6154, CEP13083-970, Campinas, SP, Brazil, and ^bLaboratory of Synthesis of Natural Products and Drugs, Institute of Chemistry, University of Campinas, CP6154, CEP13083-970, Campinas, SP, Brazil
Correspondence e-mail: aparicio@iqm.unicamp.br

In the title compound, C₁₄H₁₅NO₃, the conformation of the double bond was determined to be E, confirming the result obtained from two-dimensional NMR data. The five-membered rings of the pyrrolizine unit exhibit C-envelope conformations, with C atoms displaced from the mean planes formed by the remaining rings atoms by 0.1468 (15) and 0.5405 (17) Å. The mean planes of these rings (through all ring atoms) have a dihedral angle of 49.03 (10)°. In the crystal, molecules are linked by O-HO hydrogen bonds. The absolute configuration of the molecule was established, as judged by the, as judged by the obtained values for the Hooft and Flack parameters.

Related literature

For the preparation of the title compound, see: Freire et al. (2011). For the use of this type of compound as LFA-1 (Lymphocyte Function-Associated Antigen-1) inhibitors, see: Baumann (2007). For related structures, see: Oliveira et al. (2012a,b).

Experimental

Crystal data

C₁₄H₁₅NO₃
M_r = 245.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.5007 (3) Å
b = 13.6783 (7) Å
c = 13.8382 (7) Å
V = 1230.47 (11) Å³
Z = 4
Cu K radiation
= 0.77 mm^-1
T = 100 K
0.31 × 0.13 × 0.13 mm

Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: numerical (SADABS; Bruker, 2010) T_min = 0.924, T_max = 1.000
32528 measured reflections
2219 independent reflections
2203 reflections with I > 2(I)
R_int = 0.034

Refinement

R[F² > 2(F²)] = 0.037
wR(F²) = 0.098
S = 1.06
2219 reflections
165 parameters
H-atom parameters constrained
_max = 0.27 e Å^-3
_min = -0.23 e Å^-3
Absolute structure: Flack (1983) and Hooft et al. (2008); Hooft parameter = 0.01(2), 905 Bijvoet pairs
Flack parameter: 0.1 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O1-H1O3ⁱ	0.84	2.04	2.776 (2)	147
O3-H3O2ⁱⁱ	0.84	1.85	2.6810 (17)	168
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2526 ).

Acknowledgements

The authors acknowledge the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for financial support. FLO and KRLF were supported by bursaries from CAPES and CNPq, respectively. KRLF is currently a FAPESP post-doctoral fellow. RA and FC are recipients of research grants from CNPq.

References

Baumann, K. O. (2007). WO Patent 2007039286; Chem. Abstr. 146, 421836.
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.
Freire, K. R. L., Tormena, C. F. & Coelho, F. (2011). Synlett, 14, 2059-2063.
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96-103.
Oliveira, F. L., Freire, K. R. L., Aparicio, R. & Coelho, F. (2012a). Acta Cryst. E68, o586.
Oliveira, F. L., Freire, K. R. L., Aparicio, R. & Coelho, F. (2012b). Acta Cryst. E68, o587.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.

organic compounds