Lithium choreography: Intramolecular arylations of carbamate-stabilised carbanions and their mechanisms probed by in situ IR spectroscopy and DFT calculations

Anne M. Fournier*, Christopher J. Nichols, Mark A. Vincent, Ian H. Hillier, Jonathan Clayden

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

25 Citations (Scopus)

Abstract

Deprotonation of O-allyl, O-propargyl or O-benzyl carbamates in the presence of a lithium counterion leads to carbamate-stabilised organolithium compounds that may be quenched with electrophiles. We now report that when the allylic, propargylic or benzylic carbamate bears an N-aryl substituent, an aryl migration takes place, leading to stereochemical inversion and C-arylation of the carbamate α to oxygen. The aryl migration is an intramolecular S NAr reaction, despite the lack of anion-stabilising aryl substituents. Our in situ IR studies reveal a number of intermediates along the rearrangement pathway, including a "pre-lithiation complex," the deprotonated carbamate, the rearranged anion, and the final arylated carbamate. No evidence was obtained for a dearomatised intermediate during the aryl migration. DFT calculations predict that during the reaction the solvated Li cation moves from the carbanion centre, thus freeing its lone pair for nucleophilic attack on the remote phenyl ring. This charge separation leads to several alternative conformations. The one having Li+ bound to the carbamate oxygen gives rise to the lowest-energy transition structure, and also leads to inversion of the configuration. In agreement with the IR studies, the DFT calculations fail to locate a dearomatised intermediate. Dancing to lithium's tune: In situ IR spectroscopy and DFT calculations allow the detailed pathways of aryl migrations taking place in lithiated carbamates to be characterised (see scheme).

Original languageEnglish
Pages (from-to)16478-16490
Number of pages13
JournalChemistry - A European Journal
Volume18
Issue number51
Early online date23 Oct 2012
DOIs
Publication statusPublished - 14 Dec 2012

Keywords

  • carbamates
  • density functional calculations
  • IR spectroscopy
  • lithium
  • organolithium
  • reaction mechanisms
  • rearrangement

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