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Volume 68 
Part 12 
Pages o3392-o3393  
December 2012  

Received 2 October 2012
Accepted 13 November 2012
Online 24 November 2012

Key indicators
Single-crystal X-ray study
T = 291 K
Mean [sigma](C-C) = 0.004 Å
R = 0.053
wR = 0.149
Data-to-parameter ratio = 15.2
Details
Open access

(2aR*,5S*,6aS*,8aS*,E)-Ethyl 5-hydroxy-7,7,8a-trimethyl-8-oxo-2,2a,6,6a,7,8,8a,8b-octahydro-1H-pentaleno[1,6-bc]oxepine-4-carboxylate

aDepartment of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, India
Correspondence e-mail: gmsc@uohyd.ernet.in, gm@orgchem.iisc.ernet.in

The title compound, C17H24O5, featuring a 2-carbethoxy-3-oxepanone unit in its intramolecularly O-H...O hydrogen-bonded enol form, was obtained via [(CF3CO2)2Rh]2-catalysed intramolecular O-H bond insertion in the [alpha]-diazo-[omega]-hydroxy-[beta]-ketoester, ethyl 4-[(1S,3aS,6R,6aS)-6-hydroxy-2,2,3a-trimethyl-3-oxo-octahydropentalen-1-yl]-2-diazo-3-oxobutanoate. The seven-membered oxacyclic ring, thus constructed on a cis-fused diquinane platform, was found to adopt a distorted boat-sofa conformation.

Related literature

For rhodium carbenoid-mediated intermolecular O-H insertion reactions and their application to natural product synthesis, see: Paulissen et al. (1973[Paulissen, R., Reimlinger, H., Hayez, E., Hubert, A. J. & Teyssié, P. (1973). Tetrahedron Lett. pp. 2233-2236.]); Cox et al. (1994[Cox, G. G., Haigh, D., Hindley, R. M., Miller, D. J. & Moody, C. J. (1994). Tetrahedron Lett. 35, 3139-3142.]); Haigh (1994[Haigh, D. (1994). Tetrahedron, 50, 3177-3194.]); Aller et al. (1995[Aller, E., Brown, D. S., Cox, G. G., Miller, D. J. & Moody, C. J. (1995). J. Org. Chem. 60, 4449-4460.]); Shi et al. (1995[Shi, G.-Q., Cao, Z.-Y. & Cai, W.-L. (1995). Tetrahedron, 51, 5011-5018.]); Bulugahapitiya et al. (1997[Bulugahapitiya, P., Landais, Y., Parra-Rapado, L., Planchenault, D. & Weber, V. (1997). J. Org. Chem. 62, 1630-1641.]); Moody & Miller (1998[Moody, C. J. & Miller, D. J. (1998). Tetrahedron, 54, 2257-2268.]); Nelson et al. (2000[Nelson, T. D., Song, Z. J., Thompson, A. S., Zhao, M., DeMarco, A., Reamer, R. A., Huntington, M. F., Grabowski, E. J. J. & Reider, P. J. (2000). Tetrahedron Lett. 41, 1877-1881.]); Medeiros & Wood (2010[Medeiros, M. R. & Wood, J. L. (2010). Tetrahedron, 66, 4701-4709.]); Freeman et al. (2010[Freeman, D. B., Holubec, A. A., Weiss, M. W., Dixon, J. A., Kakefuda, A., Ohtsuka, M., Inoue, M., Vaswani, R. G., Ohki, H., Doan, B. D., Reisman, S. E., Stoltz, B. M., Day, J. J., Tao, R. N., Dieterich, N. A. & Wood, J. L. (2010). Tetrahedron, 66, 6647-6655.]); Morton et al. (2012[Morton, D., Dick, A. R., Ghosh, D. & Davies, H. M. L. (2012). Chem. Commun. 48, 5838-5840.]). For rhodium-catalysed intramolecular O-H insertion reactions, see: Paulissen et al. (1974[Paulissen, R., Hayez, E., Hubert, A. J. & Teyssié, P. (1974). Tetrahedron Lett. pp. 607-608.]); Moyer et al. (1985[Moyer, M. P., Feldman, P. L. & Rapoport, H. (1985). J. Org. Chem. 50, 5223-5230.]); Moody & Taylor (1987[Moody, C. J. & Taylor, R. J. (1987). Tetrahedron Lett. 28, 5351-5352.]); Heslin & Moody (1988[Heslin, J. C. & Moody, C. J. (1988). J. Chem. Soc. Perkin Trans. 1, pp. 1417-1423.]); Davies et al. (1990[Davies, M. J. & Moody, C. J. (1990). Synlett, pp. 95-96.]); Moody et al. (1992[Moody, C. J., Sie, E.-R. H. B. & Kulagowski, J. J. (1992). Tetrahedron, 48, 3991-4004.]); Sarabia-Garciá et al. (1994)[Sarabia-Garciá, F., López-Herrera, F. J. & Pino-González, M. S. (1994). Tetrahedron Lett. 35, 6709-6712.]; Padwa & Sá (1999[Padwa, A. & Sá, M. M. (1999). J. Braz. Chem. Soc. 10, 231-236.]); Im et al. (2005[Im, C. Y., Okuyama, T. & Sugimura, T. (2005). Chem. Lett. 34, 1328-1329.]). For reviews on rhodium-mediated C-H insertion reactions, see: Doyle et al. (2010[Doyle, M. P., Duffy, R., Ratnikov, M. & Zhou, L. (2010). Chem. Rev. 110, 704-724.]); Davies & Morton (2011[Davies, H. M. L. & Morton, D. (2011). Chem. Soc. Rev. 40, 1857-1869.]). For the construction of an angularly fused triquinane skeleton via RhII-catalysed intramolecular C-H insertion, see: Srikrishna et al. (2012[Srikrishna, A., Nagaraju, G. & Sheth, V. M. (2012). Tetrahedron, 68, 2650-2656.]). For the isolation and synthesis of penifulvin A, see: Shim et al. (2006[Shim, S. H., Swenson, D. C., Gloer, J. B., Dowd, P. F. & Wicklow, D. T. (2006). Org. Lett. 8, 1225-1228.]); Gaich & Mulzer (2009[Gaich, T. & Mulzer, J. (2009). J. Am. Chem. Soc. 131, 452-453.]); Mehta & Khan (2012[Mehta, G. & Khan, T. B. (2012). Tetrahedron Lett. 53, 4558-4561.]). For the application of p-acetamidobenzenesulfonyl azide as a diazo transfer reagent, see: Baum et al. (1987[Baum, J. S., Shook, D. A., Davies, H. M. L. & Smith, H. D. (1987). Synth. Commun. 17, 1709-1716.]). For ring conformations, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]); Boessenkool & Boeyens (1980[Boessenkool, I. K. & Boeyens, J. C. A. (1980). J. Cryst. Mol. Struct. 10, 11-18.]).

[Scheme 1]

Experimental

Crystal data
  • C17H24O5

  • Mr = 308.36

  • Orthorhombic, P b c a

  • a = 8.447 (5) Å

  • b = 18.454 (14) Å

  • c = 21.735 (15) Å

  • V = 3388 (4) Å3

  • Z = 8

  • Mo K[alpha] radiation

  • [mu] = 0.09 mm-1

  • T = 291 K

  • 0.20 × 0.18 × 0.08 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.983, Tmax = 0.993

  • 14606 measured reflections

  • 3153 independent reflections

  • 1408 reflections with I > 2[sigma](I)

  • Rint = 0.087

Refinement
  • R[F2 > 2[sigma](F2)] = 0.053

  • wR(F2) = 0.149

  • S = 0.89

  • 3153 reflections

  • 207 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.17 e Å-3

  • [Delta][rho]min = -0.17 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O2-H2O...O4 0.93 (3) 1.69 (3) 2.565 (4) 155 (3)

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2220 ).


Acknowledgements

We thank the Department of Science and Technology (DST), India, for the CCD facility at the Indian Institute of Science (IISc), Bangalore. CSAK thanks the University Grants Commission for the award of a Dr D. S. Kothari post-doctoral fellowship. GM thanks the Government of India for the award of a National Research Professorship and acknowledges the current research support from the Eli Lilly and Jubilant-Bhartia Foundations.

References

Aller, E., Brown, D. S., Cox, G. G., Miller, D. J. & Moody, C. J. (1995). J. Org. Chem. 60, 4449-4460.  [CrossRef] [ChemPort]
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  [CrossRef] [details]
Baum, J. S., Shook, D. A., Davies, H. M. L. & Smith, H. D. (1987). Synth. Commun. 17, 1709-1716.  [CrossRef] [ChemPort] [ISI]
Boessenkool, I. K. & Boeyens, J. C. A. (1980). J. Cryst. Mol. Struct. 10, 11-18.  [CrossRef] [ChemPort]
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Bulugahapitiya, P., Landais, Y., Parra-Rapado, L., Planchenault, D. & Weber, V. (1997). J. Org. Chem. 62, 1630-1641.  [CrossRef] [ChemPort]
Cox, G. G., Haigh, D., Hindley, R. M., Miller, D. J. & Moody, C. J. (1994). Tetrahedron Lett. 35, 3139-3142.  [CrossRef] [ChemPort] [ISI]
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.  [CrossRef] [ChemPort] [ISI]
Davies, M. J. & Moody, C. J. (1990). Synlett, pp. 95-96.  [CrossRef]
Davies, H. M. L. & Morton, D. (2011). Chem. Soc. Rev. 40, 1857-1869.  [ISI] [CrossRef] [ChemPort] [PubMed]
Doyle, M. P., Duffy, R., Ratnikov, M. & Zhou, L. (2010). Chem. Rev. 110, 704-724.  [ISI] [CrossRef] [PubMed] [ChemPort]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Freeman, D. B., Holubec, A. A., Weiss, M. W., Dixon, J. A., Kakefuda, A., Ohtsuka, M., Inoue, M., Vaswani, R. G., Ohki, H., Doan, B. D., Reisman, S. E., Stoltz, B. M., Day, J. J., Tao, R. N., Dieterich, N. A. & Wood, J. L. (2010). Tetrahedron, 66, 6647-6655.  [ISI] [CrossRef] [ChemPort] [PubMed]
Gaich, T. & Mulzer, J. (2009). J. Am. Chem. Soc. 131, 452-453.  [ISI] [CrossRef] [PubMed] [ChemPort]
Haigh, D. (1994). Tetrahedron, 50, 3177-3194.  [CrossRef] [ChemPort] [ISI]
Heslin, J. C. & Moody, C. J. (1988). J. Chem. Soc. Perkin Trans. 1, pp. 1417-1423.  [CrossRef]
Im, C. Y., Okuyama, T. & Sugimura, T. (2005). Chem. Lett. 34, 1328-1329.  [ISI] [CSD] [CrossRef] [ChemPort]
Medeiros, M. R. & Wood, J. L. (2010). Tetrahedron, 66, 4701-4709.  [ISI] [CrossRef] [ChemPort] [PubMed]
Mehta, G. & Khan, T. B. (2012). Tetrahedron Lett. 53, 4558-4561.  [ISI] [CSD] [CrossRef] [ChemPort]
Moody, C. J. & Miller, D. J. (1998). Tetrahedron, 54, 2257-2268.  [ISI] [CrossRef] [ChemPort]
Moody, C. J., Sie, E.-R. H. B. & Kulagowski, J. J. (1992). Tetrahedron, 48, 3991-4004.  [CrossRef] [ChemPort] [ISI]
Moody, C. J. & Taylor, R. J. (1987). Tetrahedron Lett. 28, 5351-5352.  [CrossRef] [ChemPort] [ISI]
Morton, D., Dick, A. R., Ghosh, D. & Davies, H. M. L. (2012). Chem. Commun. 48, 5838-5840.  [CSD] [CrossRef] [ChemPort]
Moyer, M. P., Feldman, P. L. & Rapoport, H. (1985). J. Org. Chem. 50, 5223-5230.  [CrossRef] [ChemPort]
Nelson, T. D., Song, Z. J., Thompson, A. S., Zhao, M., DeMarco, A., Reamer, R. A., Huntington, M. F., Grabowski, E. J. J. & Reider, P. J. (2000). Tetrahedron Lett. 41, 1877-1881.  [ISI] [CrossRef] [ChemPort]
Padwa, A. & Sá, M. M. (1999). J. Braz. Chem. Soc. 10, 231-236.  [CrossRef] [ChemPort]
Paulissen, R., Hayez, E., Hubert, A. J. & Teyssié, P. (1974). Tetrahedron Lett. pp. 607-608.  [CrossRef]
Paulissen, R., Reimlinger, H., Hayez, E., Hubert, A. J. & Teyssié, P. (1973). Tetrahedron Lett. pp. 2233-2236.  [CrossRef]
Sarabia-Garciá, F., López-Herrera, F. J. & Pino-González, M. S. (1994). Tetrahedron Lett. 35, 6709-6712.
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Shi, G.-Q., Cao, Z.-Y. & Cai, W.-L. (1995). Tetrahedron, 51, 5011-5018.  [CrossRef] [ChemPort] [ISI]
Shim, S. H., Swenson, D. C., Gloer, J. B., Dowd, P. F. & Wicklow, D. T. (2006). Org. Lett. 8, 1225-1228.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [details]
Srikrishna, A., Nagaraju, G. & Sheth, V. M. (2012). Tetrahedron, 68, 2650-2656.  [ISI] [CrossRef] [ChemPort]


Acta Cryst (2012). E68, o3392-o3393   [ doi:10.1107/S1600536812046776 ]

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