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New inter- and intramolecular carbo- and heterocyclizations of 4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-one and its η4-rhodiumcyclopentadienyl complex under the action ofn-buthyllithium: formation of functionally substituted tricyclic spirofuran and bicyclo[2.2.1]heptadiene systemscomplex under the action ofn-buthyllithium: formation of functionally substituted tricyclic spirofuran and bicyclo[2.2.1]heptadiene systems

  • Organometallic Chemistry
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Russian Chemical Bulletin Aims and scope

Abstract

Treatment with BunLi in THF (−60–0°C) causes 4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-one and itsexo-η4-coordinated (by a RhCp-group) π-diene metal complex to undergo reactions of two new types: intermolecular autocondensation-heterocyclization (affording 3,3-dichloro-3a,4′-dimethyl-4′-trichloromethyl-2,3,3a,6,7,8-hexahydrospiro-[benzofuran-2,1′-cyclohexa-2′, 5′-dien]-6-one; 24%) and intramolecular carbocyclization (yielding (η4-7,7-dichloro-1-hydroxy-4-methylbicyclo[2.2.1]hepta-2,5-diene)(η5-cyc;opentadienyl)rhodium: 77%). Both processes are assumed to involve the formation of an unusualgem-CCl2Li substitutedpara-semiquinoid intermediate, the conformation of the six-membered diene ring of which (planar or a boat-like) governs its subsequent intra- or intermolecular stereospecific carbonyl condensations.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    S. V. Sergeev, V. A. Nikanorov, D. V. Zverev & P. V. Petrovskii

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  1. S. V. Sergeev
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  2. V. A. Nikanorov
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  3. D. V. Zverev
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  4. P. V. Petrovskii
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1518–1521, August, 1997.

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Sergeev, S.V., Nikanorov, V.A., Zverev, D.V. et al. New inter- and intramolecular carbo- and heterocyclizations of 4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-one and its η4-rhodiumcyclopentadienyl complex under the action ofn-buthyllithium: formation of functionally substituted tricyclic spirofuran and bicyclo[2.2.1]heptadiene systemscomplex under the action ofn-buthyllithium: formation of functionally substituted tricyclic spirofuran and bicyclo[2.2.1]heptadiene systems. Russ Chem Bull 46, 1454–1457 (1997). https://doi.org/10.1007/BF02505685

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  • DOI: https://doi.org/10.1007/BF02505685

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