Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations

Lewis C. H. Maddock; Tracy  Nixon; Alan R. Kennedy; Michael R. Probert; William Clegg; Eva Hevia

doi:10.1002/anie.201709750

Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations

Lewis C. H. Maddock, Tracy Nixon, Alan R. Kennedy, Michael R. Probert, William Clegg, Eva Hevia

Pure And Applied Chemistry

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

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Abstract

Pairing iron bis(amide) Fe(HMDS)₂ with Na(HMDS) to form new sodium ferrate base [(dioxane)_0.5·NaFe(HMDS)₃] (1) enables regioselective mono and di-ferration (via direct Fe-H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore using excess 1 at 80^oC switches on a remarkable cascade process inducing the collective 2-fold C-H/3-fold C-F bond activations, where each C-H bond is transformed to a C-Fe bond whereas each C-F bond is transformed into a C-N bond.

Original language	English
Pages (from-to)	187-191
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	57
Issue number	1
Early online date	25 Oct 2017
DOIs	https://doi.org/10.1002/anie.201709750
Publication status	Published - 27 Dec 2017

Keywords

metallation
mixed-metal chemistry
C-F bond activation
cascade processes
ferrates

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Maddock-etal-ACIE2017-Utilising-sodium-mediated-ferration-for-regioselective-functionalisationAccepted author manuscript, 826 KB

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title = "Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations",

abstract = "Pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5·NaFe(HMDS)3] (1) enables regioselective mono and di-ferration (via direct Fe-H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore using excess 1 at 80oC switches on a remarkable cascade process inducing the collective 2-fold C-H/3-fold C-F bond activations, where each C-H bond is transformed to a C-Fe bond whereas each C-F bond is transformed into a C-N bond.",

keywords = "metallation, mixed-metal chemistry, C-F bond activation, cascade processes, ferrates",

author = "Maddock, {Lewis C. H.} and Tracy Nixon and Kennedy, {Alan R.} and Probert, {Michael R.} and William Clegg and Eva Hevia",

note = "This is the peer reviewed version of the following article: Maddock, LCH, Nixon, T, Kennedy, AR, Probert, MR, Clegg, W & Hevia, E 2017, 'Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations' Angewandte Chemie International Edition, which has been published in final form at https://doi.org/10.1002/anie.201709750. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.",

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language = "English",

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pages = "187--191",

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AU - Maddock, Lewis C. H.

AU - Nixon, Tracy

AU - Kennedy, Alan R.

AU - Probert, Michael R.

AU - Clegg, William

AU - Hevia, Eva

N1 - This is the peer reviewed version of the following article: Maddock, LCH, Nixon, T, Kennedy, AR, Probert, MR, Clegg, W & Hevia, E 2017, 'Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations' Angewandte Chemie International Edition, which has been published in final form at https://doi.org/10.1002/anie.201709750. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

PY - 2017/12/27

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N2 - Pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5·NaFe(HMDS)3] (1) enables regioselective mono and di-ferration (via direct Fe-H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore using excess 1 at 80oC switches on a remarkable cascade process inducing the collective 2-fold C-H/3-fold C-F bond activations, where each C-H bond is transformed to a C-Fe bond whereas each C-F bond is transformed into a C-N bond.

AB - Pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5·NaFe(HMDS)3] (1) enables regioselective mono and di-ferration (via direct Fe-H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore using excess 1 at 80oC switches on a remarkable cascade process inducing the collective 2-fold C-H/3-fold C-F bond activations, where each C-H bond is transformed to a C-Fe bond whereas each C-F bond is transformed into a C-N bond.

KW - metallation

KW - mixed-metal chemistry

KW - C-F bond activation

KW - cascade processes

KW - ferrates

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

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DO - 10.1002/anie.201709750

M3 - Article

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JF - Angewandte Chemie International Edition

IS - 1

ER -

Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations

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