Ligand-induced reactivity of β-diketiminate magnesium complexes for regioselective functionalization of fluoroarenes via C-H or C-F bond activations

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Abstract

Using β-diketiminate Mg(II) complexes containing either alkyl, aryl or amide groups, the regioselective functionalization of a wide range of fluoroarenes is accomplished but in uniquely different ways. Overcoming common limitations of traditional s-block bases, kinetically activated [(DippNacnac)Mg(TMP)] (1) deprotonates these molecules at room temperature, trapping sensitive fluoroaryl anions that can then engage in Negishi cross-coupling; whereas [(DippNacnac)Mg(R)THF] (R = nBu, Ph, benzofuryl) have proved to be effective reagents for C–F bond alkylation/arylation via pyridine directed C–F bond cleavage.
Original languageEnglish
Pages (from-to)11650-11653
Number of pages4
JournalChemical Communications
Issue number85
Early online date29 Sep 2017
DOIs
Publication statusPublished - 4 Nov 2017

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Thymidine Monophosphate
Alkylation
Amides
Pyridine
Magnesium
Anions
Negative ions
Chemical activation
Ligands
Molecules
Temperature
pyridine

Keywords

  • fluoroarene
  • ligand-ligand cooperation
  • metallation

Cite this

@article{75b2316cbe114ae6a2fc66f32b11690b,
title = "Ligand-induced reactivity of β-diketiminate magnesium complexes for regioselective functionalization of fluoroarenes via C-H or C-F bond activations",
abstract = "Using β-diketiminate Mg(II) complexes containing either alkyl, aryl or amide groups, the regioselective functionalization of a wide range of fluoroarenes is accomplished but in uniquely different ways. Overcoming common limitations of traditional s-block bases, kinetically activated [(DippNacnac)Mg(TMP)] (1) deprotonates these molecules at room temperature, trapping sensitive fluoroaryl anions that can then engage in Negishi cross-coupling; whereas [(DippNacnac)Mg(R)THF] (R = nBu, Ph, benzofuryl) have proved to be effective reagents for C–F bond alkylation/arylation via pyridine directed C–F bond cleavage.",
keywords = "fluoroarene, ligand-ligand cooperation, metallation",
author = "{Davin Cardona}, Laia and Ross McLellan and Kennedy, {Alan R.} and Eva Hevia",
year = "2017",
month = "11",
day = "4",
doi = "10.1039/C7CC07193K",
language = "English",
pages = "11650--11653",
journal = "Chemical Communications",
issn = "1359-7345",
number = "85",

}

TY - JOUR

T1 - Ligand-induced reactivity of β-diketiminate magnesium complexes for regioselective functionalization of fluoroarenes via C-H or C-F bond activations

AU - Davin Cardona, Laia

AU - McLellan, Ross

AU - Kennedy, Alan R.

AU - Hevia, Eva

PY - 2017/11/4

Y1 - 2017/11/4

N2 - Using β-diketiminate Mg(II) complexes containing either alkyl, aryl or amide groups, the regioselective functionalization of a wide range of fluoroarenes is accomplished but in uniquely different ways. Overcoming common limitations of traditional s-block bases, kinetically activated [(DippNacnac)Mg(TMP)] (1) deprotonates these molecules at room temperature, trapping sensitive fluoroaryl anions that can then engage in Negishi cross-coupling; whereas [(DippNacnac)Mg(R)THF] (R = nBu, Ph, benzofuryl) have proved to be effective reagents for C–F bond alkylation/arylation via pyridine directed C–F bond cleavage.

AB - Using β-diketiminate Mg(II) complexes containing either alkyl, aryl or amide groups, the regioselective functionalization of a wide range of fluoroarenes is accomplished but in uniquely different ways. Overcoming common limitations of traditional s-block bases, kinetically activated [(DippNacnac)Mg(TMP)] (1) deprotonates these molecules at room temperature, trapping sensitive fluoroaryl anions that can then engage in Negishi cross-coupling; whereas [(DippNacnac)Mg(R)THF] (R = nBu, Ph, benzofuryl) have proved to be effective reagents for C–F bond alkylation/arylation via pyridine directed C–F bond cleavage.

KW - fluoroarene

KW - ligand-ligand cooperation

KW - metallation

UR - http://dx.doi.org/10.15129/6b3146f2-fdd6-41b8-a546-ba79e8254174

UR - http://pubs.rsc.org/en/Journals/JournalIssues/CC

U2 - 10.1039/C7CC07193K

DO - 10.1039/C7CC07193K

M3 - Article

SP - 11650

EP - 11653

JO - Chemical Communications

JF - Chemical Communications

SN - 1359-7345

IS - 85

ER -