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 language | English |
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Article number | e202203074 |
Number of pages | 9 |
Journal | Chemistry - A European Journal |
Volume | 29 |
Issue number | 9 |
Early online date | 28 Oct 2022 |
DOIs | |
Publication status | Published - 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.
Funders | Funder number |
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Fonds Wetenschappelijk Onderzoek | G0D1921N |
Nederlandse Organisatie voor Wetenschappelijk Onderzoek | |
Fondation Francqui - Stichting |
Keywords
- carbene transfer
- Hieber anion
- iron catalysis
- isocyanide
- ketenimine