C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM)

Alberto Hernán-Gómez, Alan Kennedy, Eva Hevia

Research output: Contribution to journalArticle

Abstract

Combining alkali-metal mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes = [:C{N(2,4,6-Me3C6H2)CH2}2]) with group 1 alkyl bases suggest this destructive process is triggered by lateral metallation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined.
LanguageEnglish
Number of pages4
JournalAngewandte Chemie International Edition
Publication statusAccepted/In press - 19 Apr 2017

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Alkali Metals
Chemical activation
Thymidine Monophosphate
Organometallics
Complexation
Metals
Ligands
Molecules
carbene

Keywords

  • alkali-metal
  • C-N activation
  • metalation
  • mixed-metal chemistry
  • N-heterocyclic carbenes
  • SIMes

Cite this

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title = "C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM)",
abstract = "Combining alkali-metal mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes = [:C{N(2,4,6-Me3C6H2)CH2}2]) with group 1 alkyl bases suggest this destructive process is triggered by lateral metallation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined.",
keywords = "alkali-metal, C-N activation, metalation, mixed-metal chemistry, N-heterocyclic carbenes , SIMes",
author = "Alberto Hern{\'a}n-G{\'o}mez and Alan Kennedy and Eva Hevia",
note = "This is the peer reviewed version of the following article: Hern{\'a}n-G{\'o}mez, A., Kennedy, A., & Hevia, E. (2017). C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM). Angewandte Chemie International Edition. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving",
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T1 - C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM)

AU - Hernán-Gómez, Alberto

AU - Kennedy, Alan

AU - Hevia, Eva

N1 - This is the peer reviewed version of the following article: Hernán-Gómez, A., Kennedy, A., & Hevia, E. (2017). C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM). Angewandte Chemie International Edition. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving

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N2 - Combining alkali-metal mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes = [:C{N(2,4,6-Me3C6H2)CH2}2]) with group 1 alkyl bases suggest this destructive process is triggered by lateral metallation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined.

AB - Combining alkali-metal mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes = [:C{N(2,4,6-Me3C6H2)CH2}2]) with group 1 alkyl bases suggest this destructive process is triggered by lateral metallation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined.

KW - alkali-metal

KW - C-N activation

KW - metalation

KW - mixed-metal chemistry

KW - N-heterocyclic carbenes

KW - SIMes

UR - http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3773

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SN - 1433-7851

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