Deutsch
 
Hilfe Datenschutzhinweis Impressum
  DetailsucheBrowse

Datensatz

DATENSATZ AKTIONENEXPORT
  Dialkyl Ether Formation at High-Valent Nickel

Le Vaillant, F., Reijerse, E. J., Leutzsch, M., & Cornella, J. (2020). Dialkyl Ether Formation at High-Valent Nickel. Journal of the American Chemical Society, 142(46), 19540-19550. doi:10.1021/jacs.0c07381.

Item is

Basisdaten

einblenden: ausblenden:
Genre: Zeitschriftenartikel

Externe Referenzen

einblenden:

Urheber

einblenden:
ausblenden:
 Urheber:
Le Vaillant, Franck1, Autor           
Reijerse, Edward J.2, Autor
Leutzsch, Markus3, Autor           
Cornella, Josep1, Autor           
Affiliations:
1Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2466693              
2Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34−36, Mülheim an der Ruhr 45470, Germany, ou_persistent22              
3Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

Inhalt

einblenden:
ausblenden:
Schlagwörter: -
 Zusammenfassung: In this article, we investigated the I2-promoted cyclic dialkyl ether formation from 6-membered oxanickelacycles originally reported by Hillhouse. A detailed mechanistic investigation based on spectroscopic and crystallographic analysis revealed that a putative reductive elimination to forge C(sp3)–OC(sp3) using I2 might not be operative. We isolated a paramagnetic bimetallic NiIII intermediate featuring a unique Ni2(OR)2 (OR = alkoxide) diamond-like core complemented by a μ-iodo bridge between the two Ni centers, which remains stable at low temperatures, thus permitting its characterization by NMR, EPR, X-ray, and HRMS. At higher temperatures (>−10 °C), such bimetallic intermediate thermally decomposes to afford large amounts of elimination products together with iodoalkanols. Observation of the latter suggests that a C(sp3)–I bond reductive elimination occurs preferentially to any other challenging C–O bond reductive elimination. Formation of cyclized THF rings is then believed to occur through cyclization of an alcohol/alkoxide to the recently forged C(sp3)–I bond. The results of this article indicate that the use of F+ oxidants permits the challenging C(sp3)–OC(sp3) bond formation at a high-valent nickel center to proceed in good yields while minimizing deleterious elimination reactions. Preliminary investigations suggest the involvement of a high-valent bimetallic NiIII intermediate which rapidly extrudes the C–O bond product at remarkably low temperatures. The new set of conditions permitted the elusive synthesis of diethyl ether through reductive elimination, a remarkable feature currently beyond the scope of Ni.

Details

einblenden:
ausblenden:
Sprache(n): eng - English
 Datum: 2020-07-142020-11-042020-11-18
 Publikationsstatus: Erschienen
 Seiten: 11
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/jacs.0c07381
 Art des Abschluß: -

Veranstaltung

einblenden:

Entscheidung

einblenden:

Projektinformation

einblenden:

Quelle 1

einblenden:
ausblenden:
Titel: Journal of the American Chemical Society
  Andere : JACS
  Kurztitel : J. Am. Chem. Soc.
Genre der Quelle: Zeitschrift
 Urheber:
Affiliations:
Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 142 (46) Artikelnummer: - Start- / Endseite: 19540 - 19550 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870