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 journalArticlepeer-review

28 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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