Approach to 3-aminoindolin-2-ones via oxime ether functionalized carbamoylcyclohexadienes

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27 Citations (Scopus)

Abstract

O-Benzyloxime ether substituted amidocyclohexadienes were prepared in three steps in good yields from 2-aminoacetophenone. EPR spectroscopic observations and product analyses showed that peroxide-induced decompositions of model compounds led to indolin-2-ones with benzyloxyaminyl substitution at their 3-positions. The cyclization steps were very rapid and took place regioselectively at the C-atoms of the C=N bonds, by 5-exo ring closures. An O-trityloxime ether analogue was also prepared. The cyclohexadienyl intermediate smoothly yielded an alkoxylaminyl radical again by rapid 5-exo-cyclization. However, ring closure was quickly followed by another beta-scission step that released the persistent trityl radical and a 3-nitrosoindolin-2-one derivative. EPR spectroscopic evidence showed that the nitroso compound trapped other transient intermediates to afford a series of nitroxides. GC-MS analyses of products formed in reactions including methyl thioglycolate indicated that 1-benzyl-3-methyl-1,3-dihydro-2H-indol-2-one was derived from the indolinone moiety.

Original languageEnglish
Pages (from-to)5926-5933
Number of pages8
JournalThe Journal of Organic Chemistry
Volume69
DOIs
Publication statusPublished - 3 Sept 2004

Keywords

  • RADICAL ADDITION-CYCLIZATION
  • POLARITY-REVERSAL CATALYSTS
  • TRIBUTYLGERMANIUM HYDRIDE
  • SILYLATED CYCLOHEXADIENES
  • HETEROCYCLE SYNTHESIS
  • REDUCTIVE ALKYLATION
  • AMINOACYL RADICALS
  • CONCISE SYNTHESIS
  • ACTIVE OLEFINS
  • GAMMA-LACTAMS

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