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

46 Citations (Scopus)

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
Number of pages	16
Journal	Chem
Volume	9
Issue number	3
Early online date	1 Dec 2022
DOIs	https://doi.org/10.1016/j.chempr.2022.11.006
Publication status	Published - 9 Mar 2023
Externally published	Yes

Keywords

electride
mechanochemistry
sustainability
organic synthesis
Birch reduction
C-H activation
C-C coupling
benzene
pyridine

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10.1016/j.chempr.2022.11.006Licence: CC BY

1-s2.0-S2451929422006052-mainFinal published version, 3.82 MBLicence: CC BY

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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 = "electride, mechanochemistry, sustainability, organic synthesis, Birch reduction, C-H activation, C-C coupling, benzene, pyridine",

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",

year = "2023",

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

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

KW - mechanochemistry

KW - sustainability

KW - organic synthesis

KW - Birch reduction

KW - C-H activation

KW - C-C coupling

KW - benzene

KW - pyridine

U2 - 10.1016/j.chempr.2022.11.006

DO - 10.1016/j.chempr.2022.11.006

M3 - Article

SN - 2451-9294

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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