Suppressing the anionic fries rearrangement of aryl dialkylcarbamates; the isolation of a crystalline ortho-deprotonated carbamate

Felipe García, Mary McPartlin, James V. Morey, Daisuke Nobuto, Yoshinori Kondo, Hiroshi Naka, Masanobu Uchiyama, Andrew E.H. Wheatley

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

In the presence of organolithium bases phenyl dialkylcarbamates have previously been shown to undergo facile rearrangement to yield the corresponding salicylamides. However, heterometallic lithium diethyl(2,2,6,6- tetramethylpiperidido)zincate achieves the clean directed ortho-metallation (DoM) of phenyl dialkylcarbamates, with [C6H4{OC(O)- NMe2}{Zn(μ-TMP)Et}Li]2 having been structurally characterized. DFT studies point to a stepwise deprotonative mechanism in which the zincate reagent exhibits kinetic amido basicity.

Original languageEnglish
Pages (from-to)644-647
Number of pages4
JournalEuropean Journal of Organic Chemistry
Issue number4
DOIs
Publication statusPublished - 2008 Feb 12

Keywords

  • Carbamates
  • Directed ortho-metalation
  • Lithium
  • Zincates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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