A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Nathan Davison; James A. Quirk; Floriana Tuna; David Collison; Claire L. McMullin; Hannes Michaels; George H. Morritt; Paul G. Waddell; Jamie A. Gould; Marina Freitag; James A. Dawson; Erli Lu

doi:10.1016/j.chempr.2022.11.006

A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Nathan Davison, James A. Quirk, Floriana Tuna^*, David Collison, Claire L. McMullin^*, Hannes Michaels, George H. Morritt, Paul G. Waddell, Jamie A. Gould, Marina Freitag, James A. Dawson^*, Erli Lu^*

^*Corresponding author for this work

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

Abstract

In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K⁺(LiHMDS)e⁻ (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting materials (potassium metal and LiHMDS) via mechanochemical ball milling at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key diagnostic criteria for an electride, was confirmed by both experimental and computational studies. Therefore, by definition, 1 is an electride. Utilizing its anionic electrons, electride reagent 1 exhibited a versatile reactivity profile that includes (1) mediation of C–H activation and C–C coupling of benzene and pyridine and (2) mediation of solvent-free Birch reduction. This work proves the concept of facile mechanochemical synthesis of a room-temperature-stable electride, and it introduces electride 1 to the synthetic chemistry community as a versatile reagent.

Original language	English
Pages (from-to)	576-591
Journal	Chem
Volume	9
Issue number	3
DOIs	https://doi.org/10.1016/j.chempr.2022.11.006
Publication status	Published - 9 Mar 2023

Keywords

benzene
Birch reduction
C–C coupling
C–H activation
electride
mechanochemistry
organic synthesis
pyridine
SDG12: Responsible consumption and production
SDG3: Good health and well-being
sustainability

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10.1016/j.chempr.2022.11.006

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title = "A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions",

abstract = "In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K+(LiHMDS)e− (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting materials (potassium metal and LiHMDS) via mechanochemical ball milling at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key diagnostic criteria for an electride, was confirmed by both experimental and computational studies. Therefore, by definition, 1 is an electride. Utilizing its anionic electrons, electride reagent 1 exhibited a versatile reactivity profile that includes (1) mediation of C–H activation and C–C coupling of benzene and pyridine and (2) mediation of solvent-free Birch reduction. This work proves the concept of facile mechanochemical synthesis of a room-temperature-stable electride, and it introduces electride 1 to the synthetic chemistry community as a versatile reagent.",

keywords = "benzene, Birch reduction, C–C coupling, C–H activation, electride, mechanochemistry, organic synthesis, pyridine, SDG12: Responsible consumption and production, SDG3: Good health and well-being, sustainability",

author = "Nathan Davison and Quirk, {James A.} and Floriana Tuna and David Collison and McMullin, {Claire L.} and Hannes Michaels and Morritt, {George H.} and Waddell, {Paul G.} and Gould, {Jamie A.} and Marina Freitag and Dawson, {James A.} and Erli Lu",

note = "Publisher Copyright: {\textcopyright} 2022 The Author(s)",

year = "2023",

month = mar,

day = "9",

doi = "10.1016/j.chempr.2022.11.006",

language = "English",

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pages = "576--591",

journal = "Chem",

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number = "3",

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T1 - A room-temperature-stable electride and its reactivity

T2 - Reductive benzene/pyridine couplings and solvent-free Birch reductions

AU - Davison, Nathan

AU - Quirk, James A.

AU - Tuna, Floriana

AU - Collison, David

AU - McMullin, Claire L.

AU - Michaels, Hannes

AU - Morritt, George H.

AU - Waddell, Paul G.

AU - Gould, Jamie A.

AU - Freitag, Marina

AU - Dawson, James A.

AU - Lu, Erli

PY - 2023/3/9

Y1 - 2023/3/9

N2 - In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K+(LiHMDS)e− (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting materials (potassium metal and LiHMDS) via mechanochemical ball milling at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key diagnostic criteria for an electride, was confirmed by both experimental and computational studies. Therefore, by definition, 1 is an electride. Utilizing its anionic electrons, electride reagent 1 exhibited a versatile reactivity profile that includes (1) mediation of C–H activation and C–C coupling of benzene and pyridine and (2) mediation of solvent-free Birch reduction. This work proves the concept of facile mechanochemical synthesis of a room-temperature-stable electride, and it introduces electride 1 to the synthetic chemistry community as a versatile reagent.

AB - In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K+(LiHMDS)e− (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting materials (potassium metal and LiHMDS) via mechanochemical ball milling at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key diagnostic criteria for an electride, was confirmed by both experimental and computational studies. Therefore, by definition, 1 is an electride. Utilizing its anionic electrons, electride reagent 1 exhibited a versatile reactivity profile that includes (1) mediation of C–H activation and C–C coupling of benzene and pyridine and (2) mediation of solvent-free Birch reduction. This work proves the concept of facile mechanochemical synthesis of a room-temperature-stable electride, and it introduces electride 1 to the synthetic chemistry community as a versatile reagent.

KW - benzene

KW - Birch reduction

KW - C–C coupling

KW - C–H activation

KW - electride

KW - mechanochemistry

KW - organic synthesis

KW - pyridine

KW - SDG12: Responsible consumption and production

KW - SDG3: Good health and well-being

KW - sustainability

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DO - 10.1016/j.chempr.2022.11.006

M3 - Article

AN - SCOPUS:85146670045

SN - 2451-9308

VL - 9

SP - 576

EP - 591

JO - Chem

JF - Chem

IS - 3

ER -

A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Abstract

Keywords

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A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Abstract

Keywords

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EPSRC National Research Facility for Electron Paramagnetic Resonance

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