Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge

Stuart Burnett; Connor Bourne; Alexandra  M. Z. Slawin; Tanja van Mourik; Andreas Stasch

doi:10.1002/anie.202204472

Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge

Stuart Burnett, Connor Bourne, Alexandra M. Z. Slawin, Tanja van Mourik, Andreas Stasch^*

^*Corresponding author for this work

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

7 Citations (Scopus)

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Abstract

The new ß-diketimine ^iPrDipnacnacH, HC(iPrCNDip)₂H, Dip=2,6- iPr₂-C₆H₃ , was converted to the magnesium(I) complex [{(^iPrDipnacnac)Mg}₂] and reaction with 2-adamantanone (OAd) afforded the ketone-1,2-diide complex [{(^iPrDipnacnac)Mg}₂(µ -OAd)]. The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd^2- unit with long C-O bond and pyramidal carbon centre. DFT studies reveal an anionic charge on both neighbouring C and O atoms. Reductions of aliphatic ketones with magnesium(I) complexes show that these likely proceed via highly reactive dianions and afforded a 1:1 mixture of an alkoxide and an enolate when an enolisable ketone was used, and rapid CH activations reactions, e.g., of stabilising ligand moieties, when non-enolisable ketones were employed.

Original language	English
Article number	e202204472
Number of pages	10
Journal	Angewandte Chemie International Edition
Volume	61
Issue number	34
Early online date	11 Jul 2022
DOIs	https://doi.org/10.1002/anie.202204472
Publication status	Published - 16 Aug 2022

Keywords

Dianions
Low oxidation states
Magnesium
Reductions
Umpolung

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Burnett-2022-Umpolung-of-an-Aliphatic-Ketone-Angew-Chem-Int-Ed-04472-CCBY
Copyright © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.4 MBLicence: CC BY

Data underpinning Stuart Burnett's thesis
Burnett, S. (Creator) & Stasch, A. (Supervisor), University of St Andrews, 28 Jan 2025
DOI: 10.17630/57d4d24c-729d-4c0f-8bde-066d16c62cfe, https://doi.org/10.17630/sta/274
Dataset: Thesis dataset
Umpolung of an Aliphatic Ketone to a Magnesium Ketone-1,2-diide Complex with Vicinal Dianionic Charge (Dataset NMR, Computational)
Burnett, S. (Creator), Bourne, C. (Creator), Slawin, A. M. Z. (Creator), van Mourik, T. (Creator) & Stasch, A. (Creator), University of St Andrews, 27 Jul 2022
DOI: 10.17630/326e2023-ecb9-4814-90af-62caa75828a5
Dataset

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@article{68176f750c7246edad5e68d5f6270e33,

title = "Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge",

abstract = "The new {\ss}-diketimine iPrDipnacnacH, HC(iPrCNDip)2H, Dip=2,6- iPr2-C6H3 , was converted to the magnesium(I) complex [{(iPrDipnacnac)Mg}2] and reaction with 2-adamantanone (OAd) afforded the ketone-1,2-diide complex [{(iPrDipnacnac)Mg}2(µ -OAd)]. The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd2- unit with long C-O bond and pyramidal carbon centre. DFT studies reveal an anionic charge on both neighbouring C and O atoms. Reductions of aliphatic ketones with magnesium(I) complexes show that these likely proceed via highly reactive dianions and afforded a 1:1 mixture of an alkoxide and an enolate when an enolisable ketone was used, and rapid CH activations reactions, e.g., of stabilising ligand moieties, when non-enolisable ketones were employed.",

keywords = "Dianions, Low oxidation states, Magnesium, Reductions, Umpolung",

author = "Stuart Burnett and Connor Bourne and Slawin, {Alexandra M. Z.} and {van Mourik}, Tanja and Andreas Stasch",

note = "We thank the University of St Andrews and the EPSRC doctoral training grant (EP/N509759/1) for support.",

year = "2022",

month = aug,

day = "16",

doi = "10.1002/anie.202204472",

language = "English",

volume = "61",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons, Ltd",

number = "34",

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TY - JOUR

T1 - Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge

AU - Burnett, Stuart

AU - Bourne, Connor

AU - Slawin, Alexandra M. Z.

AU - van Mourik, Tanja

AU - Stasch, Andreas

N1 - We thank the University of St Andrews and the EPSRC doctoral training grant (EP/N509759/1) for support.

PY - 2022/8/16

Y1 - 2022/8/16

N2 - The new ß-diketimine iPrDipnacnacH, HC(iPrCNDip)2H, Dip=2,6- iPr2-C6H3 , was converted to the magnesium(I) complex [{(iPrDipnacnac)Mg}2] and reaction with 2-adamantanone (OAd) afforded the ketone-1,2-diide complex [{(iPrDipnacnac)Mg}2(µ -OAd)]. The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd2- unit with long C-O bond and pyramidal carbon centre. DFT studies reveal an anionic charge on both neighbouring C and O atoms. Reductions of aliphatic ketones with magnesium(I) complexes show that these likely proceed via highly reactive dianions and afforded a 1:1 mixture of an alkoxide and an enolate when an enolisable ketone was used, and rapid CH activations reactions, e.g., of stabilising ligand moieties, when non-enolisable ketones were employed.

AB - The new ß-diketimine iPrDipnacnacH, HC(iPrCNDip)2H, Dip=2,6- iPr2-C6H3 , was converted to the magnesium(I) complex [{(iPrDipnacnac)Mg}2] and reaction with 2-adamantanone (OAd) afforded the ketone-1,2-diide complex [{(iPrDipnacnac)Mg}2(µ -OAd)]. The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd2- unit with long C-O bond and pyramidal carbon centre. DFT studies reveal an anionic charge on both neighbouring C and O atoms. Reductions of aliphatic ketones with magnesium(I) complexes show that these likely proceed via highly reactive dianions and afforded a 1:1 mixture of an alkoxide and an enolate when an enolisable ketone was used, and rapid CH activations reactions, e.g., of stabilising ligand moieties, when non-enolisable ketones were employed.

KW - Dianions

KW - Low oxidation states

KW - Magnesium

KW - Reductions

KW - Umpolung

U2 - 10.1002/anie.202204472

DO - 10.1002/anie.202204472

M3 - Article

SN - 1433-7851

VL - 61

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 34

M1 - e202204472

ER -

Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge

Abstract

Keywords

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Datasets

Data underpinning Stuart Burnett's thesis

Umpolung of an Aliphatic Ketone to a Magnesium Ketone-1,2-diide Complex with Vicinal Dianionic Charge (Dataset NMR, Computational)

Cite this