Two Paths to Oxidative C-H Amination Under Basic Conditions: A Theoretical Case Study Reveals Hidden Opportunities Provided by Electron Upconversion

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Paul Eckhardt
  • Quintin Elliot
  • Igor V Alabugin
  • Till Opatz
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000847824800001&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/chem.202201637
eISSN
1521-3765
Externe Identifier
  • Clarivate Analytics Document Solution ID: 5P9CK
  • PubMed Identifier: 35880945
ISSN
0947-6539
Ausgabe der Veröffentlichung
60
Zeitschrift
CHEMISTRY-A EUROPEAN JOURNAL
Schlüsselwörter
  • C-N bond formation
  • cyclization
  • Marcus inverted region
  • radical anion
  • two-center three-electron bond
Artikelnummer
ARTN e202201637
Datum der Veröffentlichung
2022
Status
Published
Titel
Two Paths to Oxidative C-H Amination Under Basic Conditions: A Theoretical Case Study Reveals Hidden Opportunities Provided by Electron Upconversion
Sub types
  • Article
Ausgabe der Zeitschrift
28

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:title>Abstract</jats:title><jats:p>Traditionally, cross‐dehydrogenative coupling (CDC) leads to C−N bond formation under basic and oxidative conditions and is proposed to proceed via a two‐electron bond formation mediated by carbenium ions. However, the formation of such high‐energy intermediates is only possible in the presence of strong oxidants, which may lead to undesired side reactions and poor functional group tolerance. In this work we explore if oxidation under basic conditions allows the formation of three‐electron bonds (resulting in “upconverted” highly‐reducing radical‐anions). The benefit of this “upconversion” process is in the ability to use milder oxidants (e. g., O<jats:sub>2</jats:sub>) and to avoid high‐energy intermediates. Comparison of the two‐ and three‐electron pathways using quantum mechanical calculations reveals that not only does the absence of a strong oxidant shut down two‐electron pathways in favor of a three‐electron path but, paradoxically, weaker oxidants react faster with the upconverted reductants by avoiding the inverted Marcus region for electron transfer.</jats:p>
Autoren
  • Paul Eckhardt
  • Quintin Elliot
  • Igor V Alabugin
  • Till Opatz
DOI
10.1002/chem.202201637
eISSN
1521-3765
ISSN
0947-6539
Ausgabe der Veröffentlichung
60
Zeitschrift
Chemistry – A European Journal
Sprache
en
Online publication date
2022
Datum der Veröffentlichung
2022
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/chem.202201637
Datum der Datenerfassung
2023
Titel
Two Paths to Oxidative C−H Amination Under Basic Conditions: A Theoretical Case Study Reveals Hidden Opportunities Provided by Electron Upconversion**
Ausgabe der Zeitschrift
28

Datenquelle: Crossref

Abstract
Traditionally, cross-dehydrogenative coupling (CDC) leads to C-N bond formation under basic and oxidative conditions and is proposed to proceed via a two-electron bond formation mediated by carbenium ions. However, the formation of such high-energy intermediates is only possible in the presence of strong oxidants, which may lead to undesired side reactions and poor functional group tolerance. In this work we explore if oxidation under basic conditions allows the formation of three-electron bonds (resulting in "upconverted" highly-reducing radical-anions). The benefit of this "upconversion" process is in the ability to use milder oxidants (e. g., O<sub>2</sub> ) and to avoid high-energy intermediates. Comparison of the two- and three-electron pathways using quantum mechanical calculations reveals that not only does the absence of a strong oxidant shut down two-electron pathways in favor of a three-electron path but, paradoxically, weaker oxidants react faster with the upconverted reductants by avoiding the inverted Marcus region for electron transfer.
Addresses
  • Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Autoren
  • Paul Eckhardt
  • Quintin Elliot
  • Igor V Alabugin
  • Till Opatz
DOI
10.1002/chem.202201637
eISSN
1521-3765
Externe Identifier
  • PubMed Identifier: 35880945
  • PubMed Central ID: PMC9804812
Funding acknowledgements
  • Alliance for High Performance Computing in Rhineland Palatinate:
  • National Science Foundation: CHE-2102579
Open access
true
ISSN
0947-6539
Ausgabe der Veröffentlichung
60
Zeitschrift
Chemistry (Weinheim an der Bergstrasse, Germany)
Sprache
eng
Medium
Print-Electronic
Online publication date
2022
Open access status
Open Access
Paginierung
e202201637
Datum der Veröffentlichung
2022
Status
Published
Publisher licence
CC BY-NC-ND
Datum der Datenerfassung
2022
Titel
Two Paths to Oxidative C-H Amination Under Basic Conditions: A Theoretical Case Study Reveals Hidden Opportunities Provided by Electron Upconversion.
Sub types
  • research-article
  • Journal Article
Ausgabe der Zeitschrift
28

Files

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/chem.202201637 https://europepmc.org/articles/PMC9804812?pdf=render

Datenquelle: Europe PubMed Central

Abstract
Traditionally, cross-dehydrogenative coupling (CDC) leads to C-N bond formation under basic and oxidative conditions and is proposed to proceed via a two-electron bond formation mediated by carbenium ions. However, the formation of such high-energy intermediates is only possible in the presence of strong oxidants, which may lead to undesired side reactions and poor functional group tolerance. In this work we explore if oxidation under basic conditions allows the formation of three-electron bonds (resulting in "upconverted" highly-reducing radical-anions). The benefit of this "upconversion" process is in the ability to use milder oxidants (e. g., O2 ) and to avoid high-energy intermediates. Comparison of the two- and three-electron pathways using quantum mechanical calculations reveals that not only does the absence of a strong oxidant shut down two-electron pathways in favor of a three-electron path but, paradoxically, weaker oxidants react faster with the upconverted reductants by avoiding the inverted Marcus region for electron transfer.
Autoren
  • Paul Eckhardt
  • Quintin Elliot
  • Igor V Alabugin
  • Till Opatz
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/35880945
DOI
10.1002/chem.202201637
eISSN
1521-3765
Externe Identifier
  • PubMed Central ID: PMC9804812
Funding acknowledgements
  • National Science Foundation: CHE-2102579
  • Alliance for High Performance Computing in Rhineland Palatinate:
Ausgabe der Veröffentlichung
60
Zeitschrift
Chemistry
Schlüsselwörter
  • C−N bond formation
  • Marcus inverted region
  • cyclization
  • radical anion
  • two-center three-electron bond
Sprache
eng
Country
Germany
Paginierung
e202201637
Datum der Veröffentlichung
2022
Status
Published
Titel
Two Paths to Oxidative C-H Amination Under Basic Conditions: A Theoretical Case Study Reveals Hidden Opportunities Provided by Electron Upconversion.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
28

Datenquelle: PubMed

Author's licence
CC-BY-NC-ND
Autoren
  • Paul Eckhardt
  • Quintin Elliot
  • Igor V Alabugin
  • Till Opatz
Hosting institution
Universitätsbibliothek Mainz
Sammlungen
  • DFG-491381577-H
Resource version
Published version
DOI
10.1002/chem.202201637
Funding acknowledgements
  • Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 491381577
File(s) embargoed
false
Open access
true
ISSN
1521-3765
Ausgabe der Veröffentlichung
60
Zeitschrift
Chemistry - a European journal
Schlüsselwörter
  • 540 Chemie
  • 540 Chemistry and allied sciences
Sprache
eng
Open access status
Open Access
Paginierung
e202201637
Datum der Veröffentlichung
2022
Public URL
https://openscience.ub.uni-mainz.de/handle/20.500.12030/8716
Herausgeber
Wiley-VCH
Datum der Datenerfassung
2023
Datum, an dem der Datensatz öffentlich gemacht wurde
2023
Zugang
Public
Titel
Two paths to oxidative C−H amination under basic conditions : a theoretical case study reveals hidden opportunities provided by electron upconversion
Ausgabe der Zeitschrift
28

Files

two_paths_to_oxidative_ch_ami-20230127162548809.pdf

Datenquelle: OPENSCIENCE.UB

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