[Journal logo]

Volume 68 
Part 1 
Page o232  
January 2012  

Received 13 December 2011
Accepted 14 December 2011
Online 23 December 2011

Key indicators
Single-crystal X-ray study
T = 298 K
Mean [sigma](C-C) = 0.006 Å
R = 0.029
wR = 0.075
Data-to-parameter ratio = 13.1
Details
Open access

(3S*,4S*,E)-tert-Butyl 3,4-dibromo-5-oxocyclooct-1-enecarboxylate

aDepartamento de Quimica Organica, Universidad de Salamanca, Plaza de los Caidos, 37008 Salamanca, Spain, and bServicio General de Rayos X, Universidad de Salamanca, Plaza de los Caidos, 37008 Salamanca, Spain
Correspondence e-mail: nmg@usal.es

The title compound, C13H18Br2O3, was prepared by a bromination reaction of (1E,3Z)-methyl 5-oxocycloocta-1,3-dienecarboxylate, which was obtained by an epoxydation reaction of tert-butyl cyclooct-1,3-dienecarboxylate. The crystal structure confirms unequivocally the absolute configuration of both chiral centres to be S. In the crystal, C-H...O interactions link the molecules into chains running along the c axis.

Related literature

For the Michael addition of enantiomerically pure lithium amides, see: Davies et al. (2005[Davies, S. G., Smith, A. D. & Price, P. D. (2005). Tetrahedron Asymmetry, 16, 2833-2891.]). For their importance in pharmacology, see: Fülöp et al. (2001[Fülöp, F. (2001). Chem. Rev. 101, 2181-2204.]). For the reactivity of the cycloocta-1,5-diene in basic medium, see: Huber et al. (1969[Huber, A. J. & Reimlinger, H. (1969). Synthesis, pp. 97-112.], 1970[Huber, A. J. & Reimlinger, H. (1970). Synthesis, pp. 405-430.]). For the preparation of analogous unsaturated cyclooctane esters, see: Garrido et al. (2008[Garrido, N. M., Blanco, M., Cascón, I. F., Díez, D. & Vicente, V. M. (2008). Tetrahedron Asymmetry, 19, 2895-2900.]).

[Scheme 1]

Experimental

Crystal data
  • C13H18Br2O3

  • Mr = 382.09

  • Orthorhombic, P c a 21

  • a = 14.0658 (4) Å

  • b = 9.5990 (3) Å

  • c = 11.2657 (3) Å

  • V = 1521.07 (8) Å3

  • Z = 4

  • Cu K[alpha] radiation

  • [mu] = 6.76 mm-1

  • T = 298 K

  • 0.24 × 0.14 × 0.10 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.370, Tmax = 0.509

  • 10215 measured reflections

  • 2170 independent reflections

  • 2153 reflections with I > 2[sigma](I)

  • Rint = 0.048

Refinement
  • R[F2 > 2[sigma](F2)] = 0.029

  • wR(F2) = 0.075

  • S = 1.09

  • 2170 reflections

  • 166 parameters

  • 1 restraint

  • H-atom parameters constrained

  • [Delta][rho]max = 0.32 e Å-3

  • [Delta][rho]min = -0.46 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 803 Friedel pairs

  • Flack parameter: 0.06 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
C3-H3...O3i 0.98 2.57 3.525 (5) 165
C8-H8A...O3i 0.97 2.63 3.590 (6) 172
Symmetry code: (i) [-x+2, -y+2, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5753 ).


Acknowledgements

The authors are grateful to the FSE, the Spanish MICINN (EUI 2008-00173) and (CTQ 2009-11172/BQU) and the Junta de Castilla y Leon (Spain) for financial support (GR-178 and SA001A09). The authors also thank Grupo Santander for the doctoral fellowship awarded to MB.

References

Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Davies, S. G., Smith, A. D. & Price, P. D. (2005). Tetrahedron Asymmetry, 16, 2833-2891.  [ChemPort]
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [details]
Fülöp, F. (2001). Chem. Rev. 101, 2181-2204.  [ISI] [CrossRef] [PubMed] [ChemPort]
Garrido, N. M., Blanco, M., Cascón, I. F., Díez, D. & Vicente, V. M. (2008). Tetrahedron Asymmetry, 19, 2895-2900.  [CrossRef] [ChemPort]
Huber, A. J. & Reimlinger, H. (1969). Synthesis, pp. 97-112.
Huber, A. J. & Reimlinger, H. (1970). Synthesis, pp. 405-430.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.  [ISI] [CrossRef] [ChemPort] [details]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]


Acta Cryst (2012). E68, o232  [ doi:10.1107/S1600536811053852 ]

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.