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

doi:10.1002/chem.202203074

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 journal › Article › Academic › peer-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 language	English
Number of pages	9
Journal	Chemistry: a European journal
Volume	29
Early online date	28 Oct 2022
DOIs	https://doi.org/10.1002/chem.202203074
Publication status	Published - 10 Feb 2023

Keywords

Carbene transfer
Hieber anion
Iron catalysis
Isocyanide
Ketenimine

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10.1002/chem.202203074Licence: CC BY

Cite this

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title = "Iron-Catalysed Carbene Transfer to Isocyanides as a Platform for Heterocycle Synthesis",

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.",

keywords = "Carbene transfer, Hieber anion, Iron catalysis, Isocyanide, Ketenimine",

author = "Roose, {Thomas R} and Preschel, {H Daniel} and {Mayo Tejedor}, Helena and Roozee, {Jasper C} and Hamlin, {Trevor A} and Maes, {Bert U W} and Eelco Ruijter and Orru, {Romano V A}",

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doi = "10.1002/chem.202203074",

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T1 - Iron-Catalysed Carbene Transfer to Isocyanides as a Platform for Heterocycle Synthesis

AU - Roose, Thomas R

AU - Preschel, H Daniel

AU - Mayo Tejedor, Helena

AU - Roozee, Jasper C

AU - Hamlin, Trevor A

AU - Maes, Bert U W

AU - Ruijter, Eelco

AU - Orru, Romano V A

PY - 2023/2/10

Y1 - 2023/2/10

N2 - 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.

AB - 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.

KW - Carbene transfer

KW - Hieber anion

KW - Iron catalysis

KW - Isocyanide

KW - Ketenimine

U2 - 10.1002/chem.202203074

DO - 10.1002/chem.202203074

M3 - Article

C2 - 36305372

SN - 0947-6539

VL - 29

JO - Chemistry: a European journal

JF - Chemistry: a European journal

ER -