Synthesis of Mesoionic N-Heterocyclic Olefins and Catalytic Application for Hydroboration Reactions

Zhang, Zengyu; Huang, Shiqing; Huang, Liang; Zhao, Hongyan; Yan, Xiaoyu

doi:10.1021/acs.joc.0c00257

Cited by 40 publications

(40 citation statements)

References 84 publications

(42 reference statements)

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“…Most prominently, N-heterocyclic carbenes (NHCs) are established catalysts for a range of organic transformations . Other carbon nucleophiles have more recently appeared as organocatalysts, including N-heterocyclic olefins, carbodicarbenes, and carbonyl-stabilized phosphorus ylides …”

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confidence: 99%

Carbodiphosphorane-Catalyzed Hydroboration of Ketones and Imines

2021

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Carbodiphosphorane-Catalyzed Hydroboration of Ketones and Imines

2021

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“…In this regard, the synthesis, isolation and characterisation of MIOs and their compounds were recently reported. [27,28] Since the term "mesoionic" was defined in the mid twentieth century, [29] the chemistry of MIIs has been a widely established field in heterocyclic chemistry with a focus on the synthesis and gauging of the reactivity. [30,31] Many of the studied compounds were only proposed as intermediates in reactions [32] or decomposed upon generation [33,[34][35][36] while stable MIIs were almost exclusively isolated with an electron-withdrawing moiety on the exocyclic N (Scheme 1, bottom: R = EWG, L = heterocycles).…”

Section: Introductionmentioning

confidence: 99%

“…That this can be expected is corroborated by looking at the chemistry of MICs vis a vis classical NHCs. In this regard, the synthesis, isolation and characterisation of MIOs and their compounds were recently reported [27, 28] …”

Section: Introductionmentioning

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Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates

et al. 2022

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We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MIIÀ CO 2 and À Rh(CO) 2 Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituentinduced fluorine-specific interactions and undergo CÀ H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO-LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.

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“…Eine solche Entwicklung wird deutlich, wenn die Chemie von MICs vis a vis mit der Chemie klassischer NHCs verglichen wird. Im Hinblick darauf wurde erst kürzlich über die Synthese, Isolation und Charakterisierung von MIOs und deren Verbindungen berichtet [27, 28] …”

Section: Introductionunclassified

Mesoionische Imine (MIIs): Starke Donoren und vielseitige Liganden für Übergangsmetalle und Hauptgruppensubstrate

et al. 2022

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Wir berichten über die Synthese und die Reaktivität mesoionischer Imine (MIIs) des 1,2,3‐Triazolin‐5‐imin Typs. Die MIIs sind über eine Basen‐mediierte Cycloaddition eines substituierten Acetonitrils mit einem aromatischen Azid, Methylierung nach etablierten Methylierungsrouten und anschließender Deprotonierung zugänglich. C=O‐Streckschwingungen in MII−CO2− und −Rh(CO)2Cl‐Komplexen wurden bemüht um die Gesamtdonorstärke zu bestimmen. Die MIIs sind stärkere Donoren als N‐Heterocyclische Imine (NHIs). MIIs sind exzellente Liganden für Hauptgruppenelemente und Übergangsmetalle, in welchen sie Substituenten‐induzierte Fluor‐spezifische Wechselwirkungen zeigen oder C−H‐Aktvierungen eingehen. DFT‐Berechnungen haben Einblicke in die Grenzorbitale der MIIs gegeben. Die Rechnungen sagen im Vergleich zu verwandten Liganden eine relative kleine HOMO–LUMO Lücke vorraus. MIIs können potentiell sowohl als π‐Donor‐ als auch π‐Akzeptorliganden wirken. Dieser Bericht demonstiert das Potential von MIIs spannende Eigenschaften mit einem gewaltigen Zukunftspotential zu entwickeln.

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Synthesis of Mesoionic N-Heterocyclic Olefins and Catalytic Application for Hydroboration Reactions

Abstract: Mesoionic N-heterocyclic olefins have been developed, which feature high ylidic character. These compounds have been used as efficient catalysts for hydroboration of imines, nitriles, and N-heteroarenes.Article pubs.acs.org/joc

Cited by 40 publications

References 84 publications

Carbodiphosphorane-Catalyzed Hydroboration of Ketones and Imines

Carbodiphosphorane-Catalyzed Hydroboration of Ketones and Imines

Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates

Mesoionische Imine (MIIs): Starke Donoren und vielseitige Liganden für Übergangsmetalle und Hauptgruppensubstrate

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