Abstract
Hexacyclo[6.5.0.02,7.04,12.05,10.09.13]tridecane (HCTD) contains two four-membered, two five-membered and two six-membered rings fused into a cage structure which contains about 77.0 kcal/mol of strain energy. Attempts to prepare the thioketal from the diketone of HCTD led to a skeletal rearrangement to produce a cage with one four-membered, four five-membered, and two six-membered rings fused into a cage (RHCTD). The corresponding RHCTD hydrocarbon has a strain energy 13.7 kcal/mol less than that of the starting tridecane (HCTD) which provides the driving force for the rearrangement. The X-ray structures of two HCTD derivatives and one RHCTD derivative are reported. The bond lengths in the three reported structures are normal for cages of this type. The structure of tetracyclo[6.3.0.03,7.04,11]undecane-5,10-dione mono(ketene 1′,3′-propanedithioacetal) is discussed also.
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References
Watson W. H.Stereochemistry and Reactivity of Systems Containing π-Electrons;1983, VCH: Deerfield Beach, FL.
Watson, W. H.; Kashyap, R. P.; Krawiec, M.; Marchand, A. P.; Fuh-Rong, T.Struct. Chem. 1994,5, 21.
Marchand, A. P.Synlett 1991,73.
Marchand, A. P. InAdvances in Theoretically Interesting Molecules; Thummel, R. P., Ed.; JAI: Greenwich, CT,1989; Vol 1, pp. 357–399.
Marchand, A. P.; Deshpande, M. N.J. Org. Chem. 1989,54, 3226.
Marchand, A. P.; Rajapaksa, D.Tetrahedron Lett. 1993,34, 1463.
Watson, W. H.; Nagl, A.; Marchand, A. P.; Vidyasagar, V.Acta Crystallogr. 1989,C45, 1770.
Sheldrick, G. M.SHELXS86. Program for the Solution of Crystal Structures; Univ. of Göttingen: Germany,1986.
Nicolet Instrument CorporationSHELXTL for Desktop 30 (Microeclipse), Report PN269-1040340, April1986; Nicolet Instrument Corporation; WI.
International Tables for X-ray Crystallography, The Kynoch Press (Present distributor Kluwer Academic Publishers, Dordrecht);1974; Vol. IV.
PCMODEL, Serena Software, Bloomington, IN.
Spek, A. L.Acta Crystallogr. 1990,A46, C34.
Osawa, E.; Kanematsu, K. InMolecular Structure and Energetics; Liebman, J. F.; Greenberg, A., Eds.; VCH: New York; Vol. 3,1986, pp 329–369 and references cited therein.
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Kashyap, R.P., Deshpande, M.N., Rajapaksa, D. et al. Strained tridecane cage systems. J Chem Crystallogr 25, 573–578 (1995). https://doi.org/10.1007/BF01667026
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DOI: https://doi.org/10.1007/BF01667026