Atom Efficient Magnesiation of N-Substituted Alkyl Indoles with a Mixed Sodium-Magnesium Base

Michael A. Stevens, Victoria L. Blair

Research output: Contribution to journalArticleResearchpeer-review

Abstract

This study presents the alkali metal mediated magnesiation (AMMMg) of three N-alkylated indoles with the mixed Na/Mg base [(TMEDA)Na(TMP)2Mg(CH2SiMe3)] 1 (TMEDA = N,N,N′,N′-tetramethylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidine). All three magnesiated indoles have been successfully characterised by single-crystal X-ray diffraction and solution state NMR studies, whereas iodolysis and Pd-catalysed cross coupling have been investigated. The steric nature of the N-alkyl group changes the reactivity and efficiency of 1 to give either atom efficient disodium tetraindol-2-ylmagnesiates [(Na-TMEDA)2Mg(α-C9H8N)4] 2 and [(Na-TMEDA)2Mg(α-C10H11N)4] 3, or [(TMEDA)Na(TMP)(α-C11H12N)Mg(TMP)] 4, whereby only one indole molecule is selectively deprotonated.

Original languageEnglish
Pages (from-to)74-79
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Volume2018
Issue number1
DOIs
Publication statusPublished - 10 Jan 2018

Keywords

  • Cross-coupling
  • Functionalised indoles
  • Iodolysis
  • Magnesiation
  • Metallation

Cite this

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abstract = "This study presents the alkali metal mediated magnesiation (AMMMg) of three N-alkylated indoles with the mixed Na/Mg base [(TMEDA)Na(TMP)2Mg(CH2SiMe3)] 1 (TMEDA = N,N,N′,N′-tetramethylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidine). All three magnesiated indoles have been successfully characterised by single-crystal X-ray diffraction and solution state NMR studies, whereas iodolysis and Pd-catalysed cross coupling have been investigated. The steric nature of the N-alkyl group changes the reactivity and efficiency of 1 to give either atom efficient disodium tetraindol-2-ylmagnesiates [(Na-TMEDA)2Mg(α-C9H8N)4] 2 and [(Na-TMEDA)2Mg(α-C10H11N)4] 3, or [(TMEDA)Na(TMP)(α-C11H12N)Mg(TMP)] 4, whereby only one indole molecule is selectively deprotonated.",
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Atom Efficient Magnesiation of N-Substituted Alkyl Indoles with a Mixed Sodium-Magnesium Base. / Stevens, Michael A.; Blair, Victoria L.

In: European Journal of Inorganic Chemistry, Vol. 2018, No. 1, 10.01.2018, p. 74-79.

Research output: Contribution to journalArticleResearchpeer-review

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N2 - This study presents the alkali metal mediated magnesiation (AMMMg) of three N-alkylated indoles with the mixed Na/Mg base [(TMEDA)Na(TMP)2Mg(CH2SiMe3)] 1 (TMEDA = N,N,N′,N′-tetramethylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidine). All three magnesiated indoles have been successfully characterised by single-crystal X-ray diffraction and solution state NMR studies, whereas iodolysis and Pd-catalysed cross coupling have been investigated. The steric nature of the N-alkyl group changes the reactivity and efficiency of 1 to give either atom efficient disodium tetraindol-2-ylmagnesiates [(Na-TMEDA)2Mg(α-C9H8N)4] 2 and [(Na-TMEDA)2Mg(α-C10H11N)4] 3, or [(TMEDA)Na(TMP)(α-C11H12N)Mg(TMP)] 4, whereby only one indole molecule is selectively deprotonated.

AB - This study presents the alkali metal mediated magnesiation (AMMMg) of three N-alkylated indoles with the mixed Na/Mg base [(TMEDA)Na(TMP)2Mg(CH2SiMe3)] 1 (TMEDA = N,N,N′,N′-tetramethylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidine). All three magnesiated indoles have been successfully characterised by single-crystal X-ray diffraction and solution state NMR studies, whereas iodolysis and Pd-catalysed cross coupling have been investigated. The steric nature of the N-alkyl group changes the reactivity and efficiency of 1 to give either atom efficient disodium tetraindol-2-ylmagnesiates [(Na-TMEDA)2Mg(α-C9H8N)4] 2 and [(Na-TMEDA)2Mg(α-C10H11N)4] 3, or [(TMEDA)Na(TMP)(α-C11H12N)Mg(TMP)] 4, whereby only one indole molecule is selectively deprotonated.

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