Russian Chemical Bulletin

, Volume 44, Issue 3, pp 502–506 | Cite as

Redox troponization as a novel method for the synthesis of stereoisomeric Eschenmoser's oximes and related non-benzenoid aromatic systems

  • G. V. Gavrilova
  • A. A. Aleshkin
  • V. A. Nikanorov
  • D. P. Krut'ko
  • V. I. Rozenberg
  • O. A. Reutov
Organic Chemistry
  • 17 Downloads

Abstract

A novel method for the synthesis of the oxime of 4-methyl-2,4,6-cycloheptatrien-1-one (Eschenmoser's oxime) is proposed. The method involves redox enlargement of the ring of 4-dibromomethyl-4-methyl-2,5-cyclohexadien-1-one oxime through the action of Ni(PPh3)4 in DMF (in the presence of Zn). The product is formed as a mixture ofsyn- andanti-forms readily interconverting in solutions. A similar reaction of 4-methyl-4-trichloromethyl-2,5-cyclohexadien-1-one oxime afforded the dimer of agem-α-centered semiquinoid carbene (1,2-bis-(1-methyl-4-oxyimino-2,5-cyclohexadienyl)-1,2-dichloroethylene), together withsyn- andanti-isomers of 4-chloro-5-methyl-2,4,6-cycloheptatrien-1-one oxime, which are readily separable but also quickly interconverting in solutions. For the latter compounds, the complete1H NMR assignment of the stereoisomeric structures has been carried out.

Key words

non-benzenoid aromatic compounds tropones troponoximes Pd0 complexes in organic synthesis 

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Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • G. V. Gavrilova
    • 1
  • A. A. Aleshkin
    • 1
  • V. A. Nikanorov
    • 1
  • D. P. Krut'ko
    • 1
  • V. I. Rozenberg
    • 1
  • O. A. Reutov
    • 1
  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation

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