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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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Main Authors: Doll, Julianna S. (Author) , Eichelmann, Robert (Author) , Hertwig, Leif E. (Author) , Bender, Thilo (Author) , Kohler, Vincenz J. (Author) , Bill, Eckhard (Author) , Wadepohl, Hubert (Author) , Roşca, Dragoş-Adrian (Author)
Format: Article (Journal)
Language:English
Published: April 22, 2021
In: ACS catalysis
Year: 2021, Volume: 11, Issue: 9, Pages: 5593-5600
ISSN:2155-5435
DOI:10.1021/acscatal.1c00978
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acscatal.1c00978
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Author Notes:Julianna S. Doll, Robert Eichelmann, Leif E. Hertwig, Thilo Bender, Vincenz J. Kohler, Eckhard Bill, Hubert Wadepohl, and Dragoş-Adrian Roşca
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Summary: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.
Item Description:Gesehen am 03.03.2022
Physical Description:Online Resource
ISSN:2155-5435
DOI:10.1021/acscatal.1c00978

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