Abstract
2,8,10,11-Tetrachloro-12-oxahexacyclo[7,2.1.02.8.03.7.04.11.06.10]dodeca-1,9-diol is a strained cage molecule containing six five-membered rings and a four-membered ring. Twenty-five of the internal angles are less than 105° with 6 ranging from 89.5(3) to 97.4(3)°. The base promoted reaction of 3,6-dipyridyl-1,2,4,5-tetrazine with tetracyclo[6.3.0.04.11.05.9]undecane-3,6-dione yields the monoketone 6,7-[3′,6′-di(2″-pyridyl)-4′,5′-pyridizino]tetracyclo[6.3.0.04.11.05.9]-undecan-2-one. This compound crystallizes in the centrosymmetric space group P21/n with enantiomers related by a center of symmetry. In the crystal investigated the molecules are disordered with each site containing about 80% of one isomer and 20% of the enantiomer. When the ketone is hydrogenated and the product isolated, two different crystals were found to have a ratio of alcohol to ketone of .71/.29 and .75/.25 or about 3/1. The alcohol and ketone occupy the same sites, but with opposite stereochemistries.
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Aleksandrov, A. M., Kashyap, R. P., Pehk, T. J., Petrenko, A. E., and Watson, W. H. (1993)J. Org. Chem. 58, 1831.
Allinger, N. L., Yuh, Y. H., and Lii, J.-H. (1989)J. Am. Chem. Soc. 111, 8551. MM3 program from Technical Utilization Corporation, Powell, OH, Update May, 1992.
Boeyens, J. C. A., (1978)J. Cryst. Mol. Struct. 8, 317.
Fitch, A. N., and Jobic, H. (1993)J. Chem. Soc. Chem. Commun. 1516.
Haddadin, M. J., Wang, Y., Frenkel, S., Bott, S. G., Yang, L., Braterman, P. S., Carvallo, C., Marchand, A. P., Watson, W. H., Kashyap, R. P., Krawiec, M., and Bourne, S. A. (1994)Heterocycles, in press.
Marchand, A. P. (1989)Advances in Theoretically Interesting Molecules, Vol. 1, R. P. Thummel (ed.) (JAI Press, Greenwich, CT) p. 357.
Marchand, A. P. (1991)Synlett. 73.
Marchand, A. P., Annapurna, P., Flippen-Anderson, J. L., Gilardi, R., and George, C. (1988)Tetrahedron Lett. 29, 6681.
Marchand, A. P., Annappurna, P., Taylor, R. W., Simmons, D. L., Watson, W. H., and Nagl, A. (1990)Tetrahedron 46, 5077.
Molecular Structure Corporation TEXSAN. (1985)TEXRAY Structure Analysis Package. (3200 Research Forest Drive, The Woodlands, TX 77381).
PCMODEL (1988)Molecular Modeling Software for 386 Computer Serena Software, Bloomington, IN.
Sheldrick, G. M. (1986)SHELXS86. Program for the solution of crystal structures. (Univ. of Göttingen, Germany).
Spek, A. L. (1990)Acta Cryst. A46, C43.
Watson, W. H., Kashyap, R. P., Krawiec, M., Marchand, A. P., Reddy, G. M., and Gadgil, V. R. (1992)Acta Cryst. B48, 731.
Watson, W. H., Kashyap, R. P., Krawiec, M., Marchand, A. P., and Tsay, F.-R. (1994)Structural Chem., in press.
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Watson, W.H., Kashyap, R.P., Krawiec, M. et al. 2,8,10,11-tetrachloro-12-oxahexacyclo-[7.2.1.02,8.03,7.04,11.06,10]dodeca-1,9-diol and disorder and mixed crystals in a system of tetracyclo-[6.3.0.04,11.05,9]undecanone and undecanol derivatives. J Chem Crystallogr 24, 259–266 (1994). https://doi.org/10.1007/BF01670354
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DOI: https://doi.org/10.1007/BF01670354