Ligand-Free Palladium-Catalyzed Substoichiometric Base ­Mediated Carbonylation of Aryl Iodides with Alkenylboronic Acids under Ambient Conditions

Tang, Lili; Gao, Yanqun; Chen, Junjie; Yang, Linlin; Xiao, Bing; Ge, Shenguang; Ouyang, Yuejun; Han, Wei

doi:10.1055/a-2007-2958

Cited by 3 publications

(1 citation statement)

References 65 publications

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“…Additional references cited within the Supporting Information (Ref. [37][38][39][40][41][42][43][44][45][46][47][48][49][50]).…”

Section: N-alkylationmentioning

confidence: 99%

Iron‐Based Deep Eutectic Solvents: Key Players for Amide and Sulfonamide Synthesis and Alcohol Oxidation

Cicco,

Urselli,

Favia

et al. 2024

Eur J Org Chem

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A sustainable protocol has been devised for the oxidation of activated secondary alcohols to their corresponding carbonyl compounds, as well as their utilization as selective mono‐alkylating reagents for both amide and arylsulfonamide derivatives. These reactions proceed smoothly and in good yields (up to 98%) when conducted in Fe‐based deep eutectic solvents (DESs), which serve dual roles as solvents and catalysts. Operating under mild (40 °C) and aerobic conditions, these transformations are completed within a 4 h time frame. A pharmacologically relevant amide derivative, specifically a PMRT1 inhibitor, has also been successfully synthesized on a 3 g‐scale utilizing a reusable FeCl3·6H2O/glycerol Lewis acidic DES.

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“…Additional references cited within the Supporting Information (Ref. [37][38][39][40][41][42][43][44][45][46][47][48][49][50]).…”

Section: N-alkylationmentioning

confidence: 99%

Iron‐Based Deep Eutectic Solvents: Key Players for Amide and Sulfonamide Synthesis and Alcohol Oxidation

Cicco,

Urselli,

Favia

et al. 2024

Eur J Org Chem

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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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Ligand-Free Iron-Catalyzed Carbonylation of Aryl Iodides with Alkenyl Boronic Acids: Access to α,β-Unsaturated Ketones

Xu,

Chen,

Sun

et al. 2024

Org. Lett.

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The application of earth-abundant and low-toxicity iron catalysts as replacements for palladium in carbonylative coupling reactions remains challenging and largely unexplored. Reported here is a highly efficient iron-catalyzed carbonylation of aryl iodides with alkenyl boronic acids under ligand-free conditions, enabling the synthesis of α,β-unsaturated ketones even at atmospheric CO pressure. The broad applicability, including its effectiveness with α-branched enones and biologically active molecules, along with high yields and selectivity, underlines the general applicability of this catalytic system.

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Ligand-Free Palladium-Catalyzed Substoichiometric Base Mediated Carbonylation of Aryl Iodides with Alkenylboronic Acids under Ambient Conditions

Cited by 3 publications

References 65 publications

Iron‐Based Deep Eutectic Solvents: Key Players for Amide and Sulfonamide Synthesis and Alcohol Oxidation

Iron‐Based Deep Eutectic Solvents: Key Players for Amide and Sulfonamide Synthesis and Alcohol Oxidation

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

Ligand-Free Iron-Catalyzed Carbonylation of Aryl Iodides with Alkenyl Boronic Acids: Access to α,β-Unsaturated Ketones

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Ligand-Free Palladium-Catalyzed Substoichiometric Base ­Mediated Carbonylation of Aryl Iodides with Alkenylboronic Acids under Ambient Conditions

Cited by 3 publications

References 65 publications

Iron‐Based Deep Eutectic Solvents: Key Players for Amide and Sulfonamide Synthesis and Alcohol Oxidation

Iron‐Based Deep Eutectic Solvents: Key Players for Amide and Sulfonamide Synthesis and Alcohol Oxidation

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

Ligand-Free Iron-Catalyzed Carbonylation of Aryl Iodides with Alkenyl Boronic Acids: Access to α,β-Unsaturated Ketones

Contact Info

Product

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About

Ligand-Free Palladium-Catalyzed Substoichiometric Base Mediated Carbonylation of Aryl Iodides with Alkenylboronic Acids under Ambient Conditions