A Practical and Regioselective Strategy for Aromatic C–H Difunctionalization via Site-Selective C–H Thianthrenation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1813 - 1818

Published: Feb. 22, 2024

Herein, we present a novel Catellani-type reaction that employed aryl-thianthrenium salts as aryl substrates to trigger the subsequent palladium/norbornene cooperatively catalyzed progress. This strategy can achieve site-selective C–H difunctionalization of compounds without directing groups or known initiating reagent. A series functionalized syntheses bioactive molecules further demonstrated potential this strategy.

Language: Английский

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Rapid and Modular Access to Multifunctionalized 1,2-Azaborines via Palladium/Norbornene Cooperative Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9512 - 9518

Published: March 29, 2024

1,2-Azaborines, a unique class of BN-isosteres benzene, have attracted great interest across several fields. While significant advancements been made in the postfunctionalization 1,2-azaborines, challenges still exist for selective functionalization C4 position and access to 1,2-azaborines with five or six independently installed substituents. Here we report rapid modular method C3 difunctionalization using palladium/norbornene (Pd/NBE) cooperative catalysis. Enabled by C2 amide-substituted NBE, diverse 3-iodo-1,2-azaborines can be used as substrates, showing broad functional group tolerance. Besides

Language: Английский

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Catalytic ortho C–H methylation and trideuteromethylation of arylthianthrenium salts via the Catellani strategy

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3333 - 3340

Published: Jan. 1, 2024

We report a Pd/NBE cooperative catalyzed ortho C–H methylation and trideuteromethylation of arylthianthrenium salts, enabling the efficient synthesis wide variety (trideutero)methylated arenes in moderate to good yields.

Language: Английский

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Site-Selective C–H Arylation of 2-Pyridones via Pd/NBE Cooperative Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7762 - 7770

Published: May 3, 2024

The 4-aryl-2-pyridone scaffold is considered to be a privileged pharmacophore. Diversity-oriented synthesis of its derivatives pressing demand within the field medicinal chemistry. Herein, we report site-selective C–H arylation 2-pyridones via palladium/norbornene cooperative catalysis. success this research based on nucleophilicity and metalation properties exhibited by C5 position in 2-pyridones, an activated norbornene that was employed capture C5-palladation intermediate transfer it C4 position, resulting highly specific at position. This methodology showcases remarkable compatibility with readily available aryl bromides, enabling efficient diverse range functional scaffolds (46 examples) notable site selectivity, which will very useful drug discovery. Furthermore, approach successfully utilized for economically viable perlolidine analogues. Density theory calculations revealed preference bond activation 2-pyridones. In addition, insights into mechanism suggest oxidative addition reductive elimination bromides are crucial steps conversion.

Language: Английский

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Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 9, 2024

In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)-stereogenic molecules by utilizing the catalytic atroposelective Catellani-type C-H arylation/desymmetric intramolecular N-arylation cascade reaction. The enantioselectivity of protocol was proved to be tuned polarity solvent, thus providing a wide range both chiral enantiomers in moderate good yields with excellent enantiomeric excesses. Noteworthy is that strategy developed herein represents unprecedented example solvent-dictated inversion compounds.

Language: Английский

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Functionalization of Heteroarenes by the Palladium/Norbornene Cooperative Catalysis

Published: Feb. 28, 2025

Language: Английский

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Pd( II )‐Initiated Palladium/Norbornene Cooperative Catalysis

Published: Feb. 28, 2025

Language: Английский

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Enabling Aryl Chloride‐Mediated Palladium/Norbornene Cooperative Catalysis

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract While the palladium/norbornene (Pd/NBE) cooperative catalysis has become increasingly useful for arene functionalization, its substrate scope been mainly restricted to reactive aryl iodides and bromides. Despite being a more available attractive feedstock, common chlorides have not used as substrates Pd/NBE catalysis. Herein, we report first general Pd/NBE‐catalyzed vicinal difunctionalization of chlorides. Enabled by combination secondary‐amide‐substituted NBEs XPhos ligand, diverse can now undergo successful ortho alkylation, amination, acylation with different ipso terminations, including olefination, hydrogenation, alkynylation. To show utility this method, late‐stage derivatizations complex bioactive compounds sequential functionalizations polyhaloarenes achieved.

Language: Английский

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Enabling Aryl Chloride‐Mediated Palladium/Norbornene Cooperative Catalysis

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

While the palladium/norbornene (Pd/NBE) cooperative catalysis has become increasingly useful for arene functionalization, its substrate scope been mainly restricted to reactive aryl iodides and bromides. Despite being a more available attractive feedstock, common chlorides have not used as substrates Pd/NBE catalysis. Herein we report first general Pd/NBE-catalyzed vicinal difunctionalization of chlorides. Enabled by combination secondary-amide-substituted NBEs XPhos ligand, diverse can now undergo successful ortho alkylation, amination, acylation with different ipso terminations, including olefination, hydrogenation, alkynylation. To show utility this method, late-stage derivatizations complex bioactive compounds sequential functionalizations polyhaloarenes achieved.

Language: Английский

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Palladium/Norbornene Cooperative Catalysis 2-Fold C–H/C–X Coupling: Construction of Polycyclic Aromatic Hydrocarbons from Brominated Benzimidazoles

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

A palladium/norbornene (NBE)-catalyzed 2-fold C-H/C-X coupling reaction of aryl iodides is reported. Bromine-substituted benzimidazoles were chosen as electrophilic and termination reagents, the versatile polycyclic aromatic hydrocarbon products successfully obtained. The strategy overcomes challenge catalyst poisoning by heterocyclic substrates. In addition, imidazole moiety in product endowed with a localization role, thus enabling compounds to be applied wider synthetic scenario, fluorescence persisted. Furthermore, bioactivity evaluation has identified three promising leading 3b, 4e, 4i.

Language: Английский

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