Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Moritz Schubert
  • Peter Franzmann
  • Anica Wuensche von Leupoldt
  • Konrad Koszinowski
  • Katja Heinze
  • Siegfried R Waldvogel
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000368070000058&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/anie.201508035
eISSN
1521-3773
Externe Identifier
  • Clarivate Analytics Document Solution ID: DA8QF
  • PubMed Identifier: 26473303
ISSN
1433-7851
Ausgabe der Veröffentlichung
3
Zeitschrift
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Schlüsselwörter
  • arene coupling
  • C-C coupling
  • cyclization
  • molybdenum
  • oxidative coupling
Paginierung
1156 - 1159
Datum der Veröffentlichung
2016
Status
Published
Titel
Over-Oxidation as the Key Step in the Mechanism of the MoCl<sub>5</sub>-Mediated Dehydrogenative Coupling of Arenes
Sub types
  • Article
Ausgabe der Zeitschrift
55

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:title>Abstract</jats:title><jats:p>Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl<jats:sub>5</jats:sub>, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl<jats:sub>5</jats:sub> acts as a one‐electron oxidant in the absence of TiCl<jats:sub>4</jats:sub> and as two‐electron oxidant in the presence of TiCl<jats:sub>4</jats:sub>, but leads to an over‐oxidized intermediate in both cases, which protects it from side reactions. In the course of aqueous work‐up the reagent waste (Mo<jats:sup>III/IV</jats:sup> species) acts as reducing agent generating the desired organic C−C coupling product.</jats:p>
Autoren
  • Moritz Schubert
  • Peter Franzmann
  • Anica Wünsche von Leupoldt
  • Konrad Koszinowski
  • Katja Heinze
  • Siegfried R Waldvogel
DOI
10.1002/anie.201508035
eISSN
1521-3773
ISSN
1433-7851
Ausgabe der Veröffentlichung
3
Zeitschrift
Angewandte Chemie International Edition
Sprache
en
Online publication date
2015
Paginierung
1156 - 1159
Datum der Veröffentlichung
2016
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/anie.201508035
Datum der Datenerfassung
2023
Titel
Over‐Oxidation as the Key Step in the Mechanism of the MoCl<sub>5</sub>‐Mediated Dehydrogenative Coupling of Arenes
Ausgabe der Zeitschrift
55

Datenquelle: Crossref

Abstract
Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl5, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl5 acts as a one-electron oxidant in the absence of TiCl4 and as two-electron oxidant in the presence of TiCl4, but leads to an over-oxidized intermediate in both cases, which protects it from side reactions. In the course of aqueous work-up the reagent waste (Mo(III/IV) species) acts as reducing agent generating the desired organic C-C coupling product.
Addresses
  • Department of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Autoren
  • Moritz Schubert
  • Peter Franzmann
  • Anica Wünsche von Leupoldt
  • Konrad Koszinowski
  • Katja Heinze
  • Siegfried R Waldvogel
DOI
10.1002/anie.201508035
eISSN
1521-3773
Externe Identifier
  • PubMed Identifier: 26473303
Funding acknowledgements
  • Center of Innovative and Emerging Materials (CINEMA):
Open access
false
ISSN
1433-7851
Ausgabe der Veröffentlichung
3
Zeitschrift
Angewandte Chemie (International ed. in English)
Sprache
eng
Medium
Print-Electronic
Online publication date
2015
Paginierung
1156 - 1159
Datum der Veröffentlichung
2016
Status
Published
Datum der Datenerfassung
2015
Titel
Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes.
Sub types
  • Research Support, Non-U.S. Gov't
  • Journal Article
Ausgabe der Zeitschrift
55

Datenquelle: Europe PubMed Central

Abstract
Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl5, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl5 acts as a one-electron oxidant in the absence of TiCl4 and as two-electron oxidant in the presence of TiCl4, but leads to an over-oxidized intermediate in both cases, which protects it from side reactions. In the course of aqueous work-up the reagent waste (Mo(III/IV) species) acts as reducing agent generating the desired organic C-C coupling product.
Autoren
  • Moritz Schubert
  • Peter Franzmann
  • Anica Wünsche von Leupoldt
  • Konrad Koszinowski
  • Katja Heinze
  • Siegfried R Waldvogel
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/26473303
DOI
10.1002/anie.201508035
eISSN
1521-3773
Ausgabe der Veröffentlichung
3
Zeitschrift
Angew Chem Int Ed Engl
Schlüsselwörter
  • C−C coupling
  • arene coupling
  • cyclization
  • molybdenum
  • oxidative coupling
Sprache
eng
Country
Germany
Paginierung
1156 - 1159
Datum der Veröffentlichung
2016
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2016
Titel
Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes.
Sub types
  • Journal Article
  • Research Support, Non-U.S. Gov't
Ausgabe der Zeitschrift
55

Datenquelle: PubMed

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