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Synthesis and Stereochemistry of exo-4-Aminomethyltetracyclo[6.2.1.13 , 6.02 , 7]dodec-9-ene

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Abstract

Tetracyclo[6.2.1.13 , 6.02 , 7]dodec-9-ene-4-carbonitrile was synthesized by reaction of cyclopentadi- ene with stereochemically pure bicyclo[2.2.1]hept-2-ene-exo-4-carbonitrile. The preferential configuration of the adduct was proposed on the basis of the results of MMX calculations of four possible stereoisomers. Tetra- cyclo[6.2.1.13 , 6.02 , 7]dodec-9-ene-4-carbonitrile was reduced with lithium aluminum hydride to the corre- sponding aminomethyl derivative, and the latter was brought into reactions with p-toluene-, p-chlorobenzene-, and p-nitrobenzenesulfonyl chlorides, phenyl-, mesityl-, and p-tolylsulfonyl isocyanates, o-tolyl, p-tolyl- sulfonyl, and benzoyl isothiocyanates, and p-nitrophenyloxirane. The reaction with p-nitrophenyloxirane occurred in a regioselective fashion, in keeping with the Krasusky rule. N-Mesityl- and N-(p-tolylsulfonyl)- N'-(tetracyclo[6.2.1.13 , 6.02 , 7]dodec-9-en-4-exo-ylmethyl)ureas were oxidized with peroxyphthalic acid to obtain the corresponding epoxy derivatives. The structure of the products was confirmed by their IR and 1H, 1 3C, and two-dimensional NMR spectra. The structure of N-benzoyl-N'-(tetracyclo[6.2.1.13 , 6.02 , 7]dodec-9-en- 4-exo-ylmethyl)thiourea was proved by the X-ray diffraction data.

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Authors and Affiliations

  1. Dnepropetrovsk National University, Nauchnyi per. 13, Dnepropetrovsk, 49625, Ukraine

    A. O. Kas'yan

  2. Institut füur organische Chemie, Rheinisch-Westfüalische technische Hochschule, Aachen, Germany

    E. A. Golodaeva, O. V. Yuzlenko & L. I. Kas'yan

  3. Institute of Single Crystals, National Academy of Sciences of Ukraine, Khar'kov, Ukraine

    S. V. Shishkina & O. V. Shishkin

Authors
  1. A. O. Kas'yan
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  2. E. A. Golodaeva
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  3. O. V. Yuzlenko
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  4. S. V. Shishkina
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  5. O. V. Shishkin
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  6. L. I. Kas'yan
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Kas'yan, A.O., Golodaeva, E.A., Yuzlenko, O.V. et al. Synthesis and Stereochemistry of exo-4-Aminomethyltetracyclo[6.2.1.13 , 6.02 , 7]dodec-9-ene. Russian Journal of Organic Chemistry 39, 1724–1732 (2003). https://doi.org/10.1023/B:RUJO.0000019735.01576.ce

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  • DOI: https://doi.org/10.1023/B:RUJO.0000019735.01576.ce

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