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Iron-catalyzed trimerization of terminal alkynes enabled by pyrimidinediimine ligands: a regioselective method for the synthesis of 1,3,5-substituted arenes

The development of pyrimidine-based analogues of the well-known pyridinediimine (PDI) iron complexes enables access to a functional-group-tolerant methodology for the catalytic trimerization of terminal aliphatic alkynes. Remarkably, in contrast to established alkyne trimerization protocols, the 1,3...

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Bibliographische Detailangaben
Hauptverfasser: Doll, Julianna S. (VerfasserIn) , Eichelmann, Robert (VerfasserIn) , Hertwig, Leif E. (VerfasserIn) , Bender, Thilo (VerfasserIn) , Kohler, Vincenz J. (VerfasserIn) , Bill, Eckhard (VerfasserIn) , Wadepohl, Hubert (VerfasserIn) , Roşca, Dragoş-Adrian (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: April 22, 2021
In: ACS catalysis
Year: 2021, Jahrgang: 11, Heft: 9, Pages: 5593-5600
ISSN:2155-5435
DOI:10.1021/acscatal.1c00978
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acscatal.1c00978
Volltext
Verfasserangaben:Julianna S. Doll, Robert Eichelmann, Leif E. Hertwig, Thilo Bender, Vincenz J. Kohler, Eckhard Bill, Hubert Wadepohl, and Dragoş-Adrian Roşca
Beschreibung
Zusammenfassung:The development of pyrimidine-based analogues of the well-known pyridinediimine (PDI) iron complexes enables access to a functional-group-tolerant methodology for the catalytic trimerization of terminal aliphatic alkynes. Remarkably, in contrast to established alkyne trimerization protocols, the 1,3,5-substituted arenes are the main reaction products. Preliminary mechanistic investigations suggest that the enhanced π-acidity of the pyrimidine ring, combined with the hemilability of the imine groups coordinated to the iron center, facilitates this transformation. The entry point in the catalytic cycle is an isolable iron dinitrogen complex. The catalytic reaction proceeds via a 1,3-substituted metallacycle, which explains the observed 1,3,5-regioselectivity. Such a metallacycle could be isolated and represents a rare 1,3-substituted ferracycle obtained through alkyne cycloaddition.
Beschreibung:Gesehen am 03.03.2022
Beschreibung:Online Resource
ISSN:2155-5435
DOI:10.1021/acscatal.1c00978

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