New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide

J. Garcia-Alvarez, D.V. Graham, A.R. Kennedy, R.E. Mulvey, S. Weatherstone

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The first reported sodium alkyl(TMP)aluminate reagent to be synthesised and crystallographically characterised, [TMEDA·Na(µ-TMP)(µ-iBu)Al(iBu)2], reacts as an amido base towards phenylacetylene to form crystalline [(TMEDA)2·Na(µ-CCPh)(µ-iBu)Al(iBu)2]; whereas the congeneric TMEDA-stabilised lithium (TMP)aluminate exhibits dual alkyl/amido basicity in its reaction with N,N-diisopropylbenzamide to form a novel heterobimetallic-heterotrianionic crystalline complex [{PhC(O)N(iPr)2}·Li{2-[1-C(O)N(iPr)2]C6H4}{Me2NCH2CH2N(Me)CH2}Al(iBu)2], which, in addition to having an ortho-deprotonated benzamide ligand, also contains a methyl-deprotonated TMEDA ligand and a neutral benzamide molecule ligated to lithium.
LanguageEnglish
Pages3208-3210
Number of pages2
JournalChemical Communications (London)
Issue number30
DOIs
Publication statusPublished - 2006

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Alkali Metals
Thymidine Monophosphate
Amides
Lithium
Crystalline materials
Ligands
Alkalinity
Sodium
Molecules
phenyllithium
benzamide

Keywords

  • crystal structures
  • deprotonation
  • generation
  • zincation

Cite this

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title = "New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide",
abstract = "The first reported sodium alkyl(TMP)aluminate reagent to be synthesised and crystallographically characterised, [TMEDA·Na(µ-TMP)(µ-iBu)Al(iBu)2], reacts as an amido base towards phenylacetylene to form crystalline [(TMEDA)2·Na(µ-CCPh)(µ-iBu)Al(iBu)2]; whereas the congeneric TMEDA-stabilised lithium (TMP)aluminate exhibits dual alkyl/amido basicity in its reaction with N,N-diisopropylbenzamide to form a novel heterobimetallic-heterotrianionic crystalline complex [{PhC(O)N(iPr)2}·Li{2-[1-C(O)N(iPr)2]C6H4}{Me2NCH2CH2N(Me)CH2}Al(iBu)2], which, in addition to having an ortho-deprotonated benzamide ligand, also contains a methyl-deprotonated TMEDA ligand and a neutral benzamide molecule ligated to lithium.",
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author = "J. Garcia-Alvarez and D.V. Graham and A.R. Kennedy and R.E. Mulvey and S. Weatherstone",
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New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide. / Garcia-Alvarez, J.; Graham, D.V.; Kennedy, A.R.; Mulvey, R.E.; Weatherstone, S.

In: Chemical Communications (London), No. 30, 2006, p. 3208-3210.

Research output: Contribution to journalArticle

TY - JOUR

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AU - Garcia-Alvarez, J.

AU - Graham, D.V.

AU - Kennedy, A.R.

AU - Mulvey, R.E.

AU - Weatherstone, S.

PY - 2006

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N2 - The first reported sodium alkyl(TMP)aluminate reagent to be synthesised and crystallographically characterised, [TMEDA·Na(µ-TMP)(µ-iBu)Al(iBu)2], reacts as an amido base towards phenylacetylene to form crystalline [(TMEDA)2·Na(µ-CCPh)(µ-iBu)Al(iBu)2]; whereas the congeneric TMEDA-stabilised lithium (TMP)aluminate exhibits dual alkyl/amido basicity in its reaction with N,N-diisopropylbenzamide to form a novel heterobimetallic-heterotrianionic crystalline complex [{PhC(O)N(iPr)2}·Li{2-[1-C(O)N(iPr)2]C6H4}{Me2NCH2CH2N(Me)CH2}Al(iBu)2], which, in addition to having an ortho-deprotonated benzamide ligand, also contains a methyl-deprotonated TMEDA ligand and a neutral benzamide molecule ligated to lithium.

AB - The first reported sodium alkyl(TMP)aluminate reagent to be synthesised and crystallographically characterised, [TMEDA·Na(µ-TMP)(µ-iBu)Al(iBu)2], reacts as an amido base towards phenylacetylene to form crystalline [(TMEDA)2·Na(µ-CCPh)(µ-iBu)Al(iBu)2]; whereas the congeneric TMEDA-stabilised lithium (TMP)aluminate exhibits dual alkyl/amido basicity in its reaction with N,N-diisopropylbenzamide to form a novel heterobimetallic-heterotrianionic crystalline complex [{PhC(O)N(iPr)2}·Li{2-[1-C(O)N(iPr)2]C6H4}{Me2NCH2CH2N(Me)CH2}Al(iBu)2], which, in addition to having an ortho-deprotonated benzamide ligand, also contains a methyl-deprotonated TMEDA ligand and a neutral benzamide molecule ligated to lithium.

KW - crystal structures

KW - deprotonation

KW - generation

KW - zincation

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