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Aminomethylations of electron-deficient compounds—bringing iron photoredox catalysis into play

Ilic, Aleksandra LU orcid ; Strücker, Benjamin R. LU ; Johnson, Catherine E. ; Hainz, Simon ; Lomoth, Reiner and Wärnmark, Kenneth LU (2024) In Chemical Science
Abstract

The α-functionalisation of N-containing compounds is an area of broad interest in synthetic chemistry due to their presence in biologically active substances among others. Visible light-induced generation of nucleophilic α-aminoalkyl radicals as reactive intermediates that can be trapped by electron-deficient alkenes presents an attractive and mild approach to achieve said functionalisation. In this work, [Fe(iii)(phtmeimb)2]PF6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate), an N-heterocyclic carbene (NHC) complex based on Earth-abundant iron, was used as photoredox catalyst to efficiently drive the formation of α-aminoalkyl radicals from a range of different α-trimethylsilylamines and their... (More)

The α-functionalisation of N-containing compounds is an area of broad interest in synthetic chemistry due to their presence in biologically active substances among others. Visible light-induced generation of nucleophilic α-aminoalkyl radicals as reactive intermediates that can be trapped by electron-deficient alkenes presents an attractive and mild approach to achieve said functionalisation. In this work, [Fe(iii)(phtmeimb)2]PF6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate), an N-heterocyclic carbene (NHC) complex based on Earth-abundant iron, was used as photoredox catalyst to efficiently drive the formation of α-aminoalkyl radicals from a range of different α-trimethylsilylamines and their subsequent addition to a number of electron-deficient alkenes under green light irradiation. Mechanistic investigations elucidated the different reaction steps of the complete photocatalytic cycle. In terms of yields and substrate scope, we show that [Fe(iii)(phtmeimb)2]PF6 can compete with noble metal photoredox catalysts, for instance outcompeting archetypal [Ru(bpy)3]Cl2 under comparable reaction conditions, illustrating that iron photocatalysts can efficiently facilitate photoredox reactions of synthetic value.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Science
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85198126470
  • pmid:39092117
ISSN
2041-6520
DOI
10.1039/d4sc02612h
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2024 The Royal Society of Chemistry.
id
2bd6866f-bfee-4881-95fd-f66f91f80846
date added to LUP
2024-11-27 12:38:50
date last changed
2025-07-10 07:25:26
@article{2bd6866f-bfee-4881-95fd-f66f91f80846,
  abstract     = {{<p>The α-functionalisation of N-containing compounds is an area of broad interest in synthetic chemistry due to their presence in biologically active substances among others. Visible light-induced generation of nucleophilic α-aminoalkyl radicals as reactive intermediates that can be trapped by electron-deficient alkenes presents an attractive and mild approach to achieve said functionalisation. In this work, [Fe(iii)(phtmeimb)<sub>2</sub>]PF<sub>6</sub> (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate), an N-heterocyclic carbene (NHC) complex based on Earth-abundant iron, was used as photoredox catalyst to efficiently drive the formation of α-aminoalkyl radicals from a range of different α-trimethylsilylamines and their subsequent addition to a number of electron-deficient alkenes under green light irradiation. Mechanistic investigations elucidated the different reaction steps of the complete photocatalytic cycle. In terms of yields and substrate scope, we show that [Fe(iii)(phtmeimb)<sub>2</sub>]PF<sub>6</sub> can compete with noble metal photoredox catalysts, for instance outcompeting archetypal [Ru(bpy)<sub>3</sub>]Cl<sub>2</sub> under comparable reaction conditions, illustrating that iron photocatalysts can efficiently facilitate photoredox reactions of synthetic value.</p>}},
  author       = {{Ilic, Aleksandra and Strücker, Benjamin R. and Johnson, Catherine E. and Hainz, Simon and Lomoth, Reiner and Wärnmark, Kenneth}},
  issn         = {{2041-6520}},
  language     = {{eng}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Chemical Science}},
  title        = {{Aminomethylations of electron-deficient compounds—bringing iron photoredox catalysis into play}},
  url          = {{http://dx.doi.org/10.1039/d4sc02612h}},
  doi          = {{10.1039/d4sc02612h}},
  year         = {{2024}},
}