Heterocyclic Carbene Catalysis

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closed (31 August 2024)

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31 December 2025

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Topic Information

Dear Colleagues,

Heterocyclic carbene catalysis is a powerful process that has experienced rapid development. In particular, N-heterocycle carbenes (NHC), which have been applied in wide areas of organic synthesis. Their use in catalysis for the formation of new bonds via umpolung or non-umpolung mechanisms has developed in the last decade, involving several intermediates and allowing a fairly wide use of this type of catalysis. Recent applications have been reported in total natural synthesis with stereo and regioselectivity. We believe that the use of these intermediates or ligands will increase.

This Topic aims to review new methods and recent developments for the synthesis of complexes with heterocyclic carbene ligands and their use for the synthesis of various molecules of interest.

Prof. Dr. Sabine Berteina-Raboin
Prof. Dr. Thierry Besson
Prof. Dr. Patrick Rollin
Topic Editors

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Participating Journals

Journal Name	Impact Factor	CiteScore	Launched Year	First Decision (median)	APC
Catalysts catalysts	3.8	6.8	2011	12.9 Days	CHF 2700	Submit
Chemistry chemistry	2.4	3.2	2019	13.4 Days	CHF 1800	Submit
Inorganics inorganics	3.1	2.8	2013	14.7 Days	CHF 2700	Submit
Molbank molbank	0.6	0.7	1997	13.9 Days	CHF 500	Submit
Molecules molecules	4.2	7.4	1996	15.1 Days	CHF 2700	Submit
Polymers polymers	4.7	8.0	2009	14.5 Days	CHF 2700	Submit

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Published Papers (6 papers)

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All Catalysts Chemistry Inorganics Molbank Molecules Polymers

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Supplementary material:
Supplementary File 1 (PDF, 984 KiB)
Supplementary File 2 (MOL, 3 KiB)
Supplementary File 3 (INCHI, 1 KiB)
Supplementary File 4 (MOL, 3 KiB)

5 pages, 552 KiB  

Open AccessShort Note

Chloro(η²,η²-cycloocta-1,5-diene){1-benzyl-3-[(S)-2-hydroxy-1-methylethyl]benzimidazol-2-ylidene}rhodium(I)

by Satoshi Sakaguchi and Shogo Matsuo

Molbank 2024, 2024(2), M1811; https://doi.org/10.3390/M1811 - 19 Apr 2024

Viewed by 849

Abstract

Previously, we demonstrated the synthesis of a well-defined hydroxyalkyl-functionalized N-heterocyclic carbene (NHC)/Ru(II) complex through the transmetalation reaction between [RuCl₂(p-cymene)]₂ and the corresponding NHC/Ag(I) complex derived from a chiral benzimidazolium salt using the Ag₂O method. In [...] Read more.

Previously, we demonstrated the synthesis of a well-defined hydroxyalkyl-functionalized N-heterocyclic carbene (NHC)/Ru(II) complex through the transmetalation reaction between [RuCl₂(p-cymene)]₂ and the corresponding NHC/Ag(I) complex derived from a chiral benzimidazolium salt using the Ag₂O method. In this study, we successfully synthesized [RhX(cod)(NHC)] complexes through a one-pot deprotonation route. The hydroxyalkyl-substituted benzimidazolium salt reacted with [Rh(OH)(cod)]₂ in THF at room temperature, affording the corresponding monodentate NHC/Rh(I) complex in nearly quantitative yield. The rhodium complex was characterized using NMR, HRMS measurement, and elemental analysis. Full article

(This article belongs to the Topic Heterocyclic Carbene Catalysis)

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Scheme 1

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Supplementary material:
Supplementary File 1 (PDF, 1788 KiB)
Supplementary File 2 (MOL, 4 KiB)
Supplementary File 3 (INCHI, 1 KiB)
Supplementary File 4 (MOL, 4 KiB)

5 pages, 640 KiB  

Open AccessShort Note

Chloro(η²,η²-cycloocta-1,5-diene){1-[(2-[(S)-1-(hydroxymethyl)-3-methylbutyl]amino)-2-oxoethyl]-3-(1-naphthalenylmethyl)benzimidazol-2-ylidene}rhodium(I)

by Satoshi Sakaguchi and Shogo Matsuo

Molbank 2024, 2024(2), M1810; https://doi.org/10.3390/M1810 - 19 Apr 2024

Viewed by 938

Abstract

Commercially available and air- and moisture-stable rhodium complex [Rh(OH)(cod)]₂ (2) was utilized in the synthesis of [RhX(cod)(NHC)] (3). The presence of an OH group in complex 2 serves as an internal base, facilitating the deprotonation of the C–H [...] Read more.

Commercially available and air- and moisture-stable rhodium complex [Rh(OH)(cod)]₂ (2) was utilized in the synthesis of [RhX(cod)(NHC)] (3). The presence of an OH group in complex 2 serves as an internal base, facilitating the deprotonation of the C–H bond of the azolium ring in the hydroxyamide-substituted benzimidazolium salt 1. This reaction between 1 and 2 proceeded in THF at room temperature without temperature control, affording the desired NHC/Rh complex 3 in excellent yield. The characterization of complex 3 was accomplished through NMR and HRMS analyses, revealing its existence as a diastereomeric mixture of two NHC/Rh complexes. Furthermore, its catalytic performance was briefly evaluated in the reaction between 2-naphthaldehyde (5) and phenylboronic acid (6). Full article

(This article belongs to the Topic Heterocyclic Carbene Catalysis)

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Scheme 1

32 pages, 9114 KiB  

Open AccessReview

Recent Advances in the Synthesis of 3,4-Dihydropyran-2-Ones Organocatalyzed by N-Heterocyclic Carbenes

by Camilo Morales-Manrique, Edwin A. Baquero and James Guevara-Pulido

Molecules 2023, 28(9), 3743; https://doi.org/10.3390/molecules28093743 - 26 Apr 2023

Cited by 2 | Viewed by 2369

Abstract

In recent years, N-heterocyclic carbenes (NHC) have gained recognition as versatile molecules capable of acting as organocatalysts in various reactions, particularly through the activation of aldehydes via Breslow-type adducts. This organocatalytic activation has enabled the production of numerous 3,4-dihydropyran-2-ones and related derivatives. [...] Read more.

In recent years, N-heterocyclic carbenes (NHC) have gained recognition as versatile molecules capable of acting as organocatalysts in various reactions, particularly through the activation of aldehydes via Breslow-type adducts. This organocatalytic activation has enabled the production of numerous 3,4-dihydropyran-2-ones and related derivatives. In this review, we provide an overview of the production of 3,4-dihydropyran-2-ones and derivatives via organocatalytic processes involving NHCs over the past eight years. These processes involve the use of a diverse range of substrates, catalysts, and reaction conditions, which can be classified into [4+2]-and [3+3]-type cycloadditions, primarily aimed at synthesizing this skeleton due to its biological activity and multiple stereocenters. These processes are scaled up to the gram scale, and the resulting products are often directed towards epimerization and functionalization to produce more complex molecules with potential applications in the biological field. Finally, we provide a perspective and the future directions of this topic in organic synthesis. Full article

(This article belongs to the Topic Heterocyclic Carbene Catalysis)

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Supplementary material:
Supplementary File 1 (ZIP, 350 KiB)
Supplementary File 2 (MOL, 1 KiB)
Supplementary File 3 (INCHI, 487 B)
Supplementary File 4 (MOL, 1 KiB)
Supplementary File 5 (CIF, 322 KiB)

5 pages, 1544 KiB  

Open AccessCommunication

Crystal Structure of 2-[(1E)-2-(4-Fluorophenyl)diazenyl]-1H-imidazole

by Thomas Gelbrich, Klaus Wurst, Paul Mayer, Herwig Schottenberger and Sven Nerdinger

Molbank 2023, 2023(1), M1571; https://doi.org/10.3390/M1571 - 1 Feb 2023

Viewed by 1153

Abstract

The molecule of the title compound adopts a twisted geometry with a rotation of approximately 30° between the mean planes of the imidazole and phenyl rings. The crystal structure displays hydrogen bonded chains as a result of N–H···N interactions between the imidazole rings [...] Read more.

The molecule of the title compound adopts a twisted geometry with a rotation of approximately 30° between the mean planes of the imidazole and phenyl rings. The crystal structure displays hydrogen bonded chains as a result of N–H···N interactions between the imidazole rings of neighboring molecules. These H-bonded chains are assembled into flat molecular layers parallel to the (121) plane. Two intermolecular interactions, involving inversion-related molecules belonging to adjacent molecular layers, contribute significantly to the stabilization of the crystal. Full article

(This article belongs to the Topic Heterocyclic Carbene Catalysis)

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Supplementary material:
Supplementary File 1 (ZIP, 7107 KiB)

16 pages, 12689 KiB  

Open AccessArticle

Influence of Substituents in a Six-Membered Chelate Ring of HG-Type Complexes Containing an N→Ru Bond on Their Stability and Catalytic Activity

by Kirill A. Vasilyev, Alexandra S. Antonova, Nikita S. Volchkov, Nikita A. Logvinenko, Eugeniya V. Nikitina, Mikhail S. Grigoriev, Anton P. Novikov, Vladimir V. Kouznetsov, Kirill B. Polyanskii and Fedor I. Zubkov

Molecules 2023, 28(3), 1188; https://doi.org/10.3390/molecules28031188 - 25 Jan 2023

Cited by 3 | Viewed by 2179

Abstract

An efficient approach to the synthesis of olefin metathesis HG-type catalysts containing an N→Ru bond in a six-membered chelate ring was proposed. For the most part, these ruthenium chelates can be prepared easily and in high yields based on the interaction between 2-vinylbenzylamines [...] Read more.

An efficient approach to the synthesis of olefin metathesis HG-type catalysts containing an N→Ru bond in a six-membered chelate ring was proposed. For the most part, these ruthenium chelates can be prepared easily and in high yields based on the interaction between 2-vinylbenzylamines and Ind II (the common precursor for Ru-complex synthesis). It was demonstrated that the increase of the steric volume of substituents attached to the nitrogen atom and in the α-position of the benzylidene fragment leads to a dramatic decrease in the stability of the target ruthenium complexes. The bulkiest ⁱPr substituent bonded to the nitrogen atom or to the α-position does not allow the closing of the chelate cycle. N,N-Diethyl-1-(2-vinylphenyl)propan-1-amine is a limiting case; its interaction with Ind II makes it possible to isolate the corresponding ruthenium chelate in a low yield (5%). Catalytic activity of the synthesized complexes was tested in RCM reactions and compared with α-unsubstituted catalysts obtained previously. The structural peculiarities of the final ruthenium complexes were thoroughly investigated using XRD and NMR analysis, which allowed making a reliable correlation between the structure of the complexes and their catalytic properties. Full article

(This article belongs to the Topic Heterocyclic Carbene Catalysis)

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Supplementary material:
Supplementary File 1 (PDF, 853 KiB)
Supplementary File 2 (MOL, 2 KiB)
Supplementary File 4 (MOL, 2 KiB)

5 pages, 382 KiB  

Open AccessCommunication

Ultrasound Assisted One-Pot Synthesis of Novel 3-(Aryl)-5-((4-(phenyldiazenyl)phenoxy)methyl)isoxazolines in Water

by Ayoub El Mahmoudi, Khalid Karrouchi, Hamza Tachallait and Khalid Bougrin

Molbank 2022, 2022(4), M1529; https://doi.org/10.3390/M1529 - 17 Dec 2022

Cited by 1 | Viewed by 1715

Abstract

In this work, we present an efficient one-pot method for the synthesis of three new azo-isoxazoline derivatives (4a–c) from aromatic aldehydes, hydroxylamine hydrochloride and 4-(allyloxy)azobenzene. Thus, the azo-isoxazoline derivatives (4a–c) were synthesized via 1,3-dipolar cycloaddition [...] Read more.

In this work, we present an efficient one-pot method for the synthesis of three new azo-isoxazoline derivatives (4a–c) from aromatic aldehydes, hydroxylamine hydrochloride and 4-(allyloxy)azobenzene. Thus, the azo-isoxazoline derivatives (4a–c) were synthesized via 1,3-dipolar cycloaddition using sodium dichloroisocyanurate (SDIC) as an eco-friendly and inexpensive oxidizing agent under ultrasound cavitation in water as a green solvent. The desired compounds 4a–c were obtained in high to excellent yields of 75–90%. Full article

(This article belongs to the Topic Heterocyclic Carbene Catalysis)

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Scheme 1

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