Iron-Catalysed Carbene Transfer to Isocyanides as a Platform for Heterocycle Synthesis

Thomas R. Roose, H. Daniel Preschel, Helena Mayo Tejedor, Jasper C. Roozee, Trevor A. Hamlin*, Bert U.W. Maes, Eelco Ruijter, Romano V.A. Orru

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

An iron-catalysed carbene transfer reaction of diazo compounds to isocyanides has been developed. The resulting ketenimines are trapped in situ with various bisnucleophiles to access a range of densely functionalized heterocycles (pyrimidinones, dihydropyrazolones, 1H-tetrazoles) in a one-pot process. The electron-rich Hieber anion ([Fe(CO)3NO]) facilitates efficient catalytic carbene transfer from acceptor-type α-diazo carbonyl compounds to isocyanides, providing a cost-efficient and benign alternative to similar noble metal-catalysed processes. Based on DFT calculations a plausible reaction mechanism for activation of the α-diazo carbonyl carbene precursor and ketenimine formation is provided.

Original languageEnglish
Article numbere202203074
Number of pages9
JournalChemistry - A European Journal
Volume29
Issue number9
Early online date28 Oct 2022
DOIs
Publication statusPublished - 10 Feb 2023

Bibliographical note

Funding Information:
This work was financially supported by the Netherlands Organisation for Scientific Research (NWO, ECHO) and the Fund for Scientific Research – Flanders (FWO, G0D1921N). B.U.W.M. thanks the Francqui Foundation for an appointment as Collen‐Francqui professor. We also kindly thank Elwin Janssen (VU Amsterdam) for NMR support.

Publisher Copyright:
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Funding

This work was financially supported by the Netherlands Organisation for Scientific Research (NWO, ECHO) and the Fund for Scientific Research – Flanders (FWO, G0D1921N). B.U.W.M. thanks the Francqui Foundation for an appointment as Collen‐Francqui professor. We also kindly thank Elwin Janssen (VU Amsterdam) for NMR support.

FundersFunder number
Fonds Wetenschappelijk OnderzoekG0D1921N
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Fondation Francqui - Stichting

    Keywords

    • carbene transfer
    • Hieber anion
    • iron catalysis
    • isocyanide
    • ketenimine

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