Selective Buchwald–Hartwig arylation of<i>C</i>-amino-1,2,4-triazoles and other coordinating aminoheterocycles enabled by bulky NHC ligands and TPEDO activator

Aстахов, А. В.; Chernenko, Andrey Yu.; Kutyrev, Vadim V.; Ranny, Gleb S.; Minyaev, Mikhail E.; Чернышев, В. М.; Ananikov, Valentine P.

doi:10.1039/d2qi01832b

Cited by 7 publications

(2 citation statements)

References 129 publications

(226 reference statements)

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“…The following supporting information is available: general experimental information, synthetic procedures and characterization of isolated compounds, additional experimental and DFT data, copies of NMR spectra and crystallographic data in CIF or other electronic format see: DOI:10.1002/###.20230XXX. The following additional references have been cited within the Supporting Information [41–77] …”

Section: Supporting Informationmentioning

confidence: 99%

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

Chernenko,

Baydikova,

Kutyrev

et al. 2024

ChemCatChem

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Aryl chlorides, due to their affordability and accessibility, are preferred reagents in Pd‐catalyzed arylation reactions. However, the reactivity of aryl chlorides is often reduced compared to aryl bromides and iodides due to the significantly higher barriers of the oxidative addition stage. This research introduces a novel design for NHC ligands, which notably enhances the efficiency of Pd/NHC catalytic systems in reactions where oxidative addition of aryl chloride is the rate‐limiting step. This design leverages a synergy between specific steric characteristics and the anionic nature of the newly fashioned 1,2,4‐triazol‐5‐ylidene ligands. These ligands, inspired by Nitron‐type designs, can be ionized under basic conditions due to their NH‐acidic aryl(alkyl)amino groups. Detailed experimental and DFT studies revealed that the deprotonation of these NHCs promotes electron donation to the metal center, promoting the oxidative addition of aryl chloride. The specially optimized ATPr ligand, featuring 2,6‐diisopropylphenyl groups, displayed remarkable catalytic efficacy in the Suzuki‐Miyaura reaction and improved outcomes in ketone α‐arylation and Buchwald‐Hartwig reactions with unactivated aryl chlorides. The insights and strategies established in this study provide rational considerations for further advancements in NHC designs and their applications in metal‐catalyzed reactions.

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Section: Supporting Informationmentioning

confidence: 99%

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

Chernenko,

Baydikova,

Kutyrev

et al. 2024

ChemCatChem

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“…The Buchwald-Hartwig amination (BHA) is one of the most efficient cross-coupling reactions to access a wide range of N-monoand N,N-disubstituted aryl amines. Despite noticeable advances in this area [35][36][37][38][39], coupling heteroaromatic amines with arylhalides is still a challenging transformation that often requires time-consuming searches for optimal conditions and catalytic systems [40][41][42][43][44][45][46][47]. In our previous study, we revealed that palladium complex with expanded-ring NHC ligand (THP-Dipp)Pd(cinn)Cl (er-NHC-Pd) is the most competent catalyst in the BHA reaction for low-reactive 5-amino-1,2,3-triazoles [32].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 5-(Aryl)amino-1,2,3-triazole-containing 2,1,3-Benzothiadiazoles via Azide–Nitrile Cycloaddition Followed by Buchwald–Hartwig Reaction

Gribanov,

Philippova,

Topchiy

et al. 2024

Molecules

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An efficient access to the novel 5-(aryl)amino-1,2,3-triazole-containing 2,1,3-benzothiadiazole derivatives has been developed. The method is based on 1,3-dipolar azide–nitrile cycloaddition followed by Buchwald–Hartwig cross-coupling to afford the corresponding N-aryl and N,N-diaryl substituted 5-amino-1,2,3-triazolyl 2,1,3-benzothiadiazoles under NHC-Pd catalysis. The one-pot diarylative Pd-catalyzed heterocyclization opens the straightforward route to triazole-linked carbazole-benzothiadiazole D-A systems. The optical and electrochemical properties of the compound obtained were investigated to estimate their potential application as emissive layers in OLED devises. The quantum yield of photoluminescence (PLQY) of the synthesized D-A derivatives depends to a large extent on electron-donating strengths of donor (D) component, reaching in some cases the values closed to 100%. Based on the most photoactive derivative and wide bandgap host material mCP, a light-emitting layer of OLED was made. The device showed a maximum brightness of 8000 cd/m2 at an applied voltage of 18 V. The maximum current efficiency of the device reaches a value of 3.29 cd/A.

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A Simple Protocol for the C−N Cross‐Coupling of Aryl Chlorides with Amines Applying Ni/NHC Catalysis

et al. 2023

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An efficient protocol for the C−N cross‐coupling of aryl chlorides with (hetero)aryl‐ and alkyl amines under nickel catalysis has been developed. The main advantage of the protocol is the use of a self‐activated Ni/NHC catalytic system generated in situ from readily available bench‐stable air‐tolerant precursors: NiCl2Py2, IPr ⋅ HCl, and sodium tert‐butoxide. A mass spectrometry mechanistic study of the reaction system revealed the dynamics of competitive processes of Ni/NHC active species formation and degradation involving NHC reductive elimination reactions and tert‐butoxide base. Optimization of the NiCl2Py2/IPr ⋅ HCl/tBuONa ratio and the reaction temperature allowed efficient catalysis to be achieved. The developed simple protocol represents an alternative for methods relying on the use of air‐sensitive and unstable Ni(cod)2 or expensive well‐defined Ni/NHC precatalysts.

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Selective Buchwald–Hartwig arylation ofC-amino-1,2,4-triazoles and other coordinating aminoheterocycles enabled by bulky NHC ligands and TPEDO activator

Abstract: A facile method for selective N-(hetero)arylation of coordinating 3(5)-amino-1,2,4-triazoles under Pd/NHC catalysis using TPEDO as a new efficient Pd(ii) to Pd(0) reductant has been developed.

Cited by 7 publications

References 129 publications

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

Synthesis of 5-(Aryl)amino-1,2,3-triazole-containing 2,1,3-Benzothiadiazoles via Azide–Nitrile Cycloaddition Followed by Buchwald–Hartwig Reaction

A Simple Protocol for the C−N Cross‐Coupling of Aryl Chlorides with Amines Applying Ni/NHC Catalysis

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