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

doi:10.1039/b606080c

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

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

40 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.

Original language	English
Pages (from-to)	3208-3210
Number of pages	2
Journal	Chemical Communications (London)
Issue number	30
DOIs	https://doi.org/10.1039/b606080c
Publication status	Published - 2006

Keywords

crystal structures
deprotonation
generation
zincation

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10.1039/b606080c

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@article{651900e0fcd34262813572a6e8470b66,

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.",

keywords = "crystal structures, deprotonation, generation, zincation",

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

year = "2006",

doi = "10.1039/b606080c",

language = "English",

pages = "3208--3210",

journal = "Chemical Communications (London)",

issn = "0009-241X",

publisher = "Royal Society of Chemistry",

number = "30",

}

TY - JOUR

T1 - New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide

AU - Garcia-Alvarez, J.

AU - Graham, D.V.

AU - Kennedy, A.R.

AU - Mulvey, R.E.

AU - Weatherstone, S.

PY - 2006

Y1 - 2006

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

UR - http://dx.doi.org/10.1039/b606080c

U2 - 10.1039/b606080c

DO - 10.1039/b606080c

M3 - Article

SN - 0009-241X

SP - 3208

EP - 3210

JO - Chemical Communications (London)

JF - Chemical Communications (London)

IS - 30

ER -

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

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Mixed-Metal Molecular Synergy and its Application in Inverse Crown Chemistry

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

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Mixed-Metal Molecular Synergy and its Application in Inverse Crown Chemistry

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