Palladium-Catalyzed Modular Synthesis of Thiophene-Fused Polycyclic Aromatics via Sequential C–H Activation

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

Published: Jan. 29, 2025

A palladium-catalyzed Catellani-type [2+2+2] annulation reaction of aryl iodides, bromothiophenes, and norbornadiene, which proceeds via a tandem Heck coupling/double C-H bond activation retro-Diels-Alder pathway to access thiophene-fused polyaromatics, is reported. The key feature this protocol represents NBD/NBE retaining annulation.

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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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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Photoactivation of Thianthrenium Salts: An Electron-Donor–Acceptor (EDA)-Complex Approach

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Thianthrenium salts have emerged as one of the most versatile reagents, gaining significant popularity within synthetic community for their utility in construction C-C and C-X (X = N, O, S, P, halogens) bonds. The use photoredox transition metal catalysis with thianthrenium C-heteroatom bond formation is well established. However, these methods require elevated temperatures, expensive catalysts, ligands under stringent conditions effective execution. In contrast, photocatalysis- transition-metal-free approaches constructing bonds using salt derivatives become increasingly sought after. this regard, electron-donor-acceptor (EDA)-complex reactions a powerful strategy organic synthesis, eliminating need photocatalysts visible light irradiation. EDA-complex photochemistry exploits electron-acceptor properties salts, facilitating rapid generation radical intermediates via C-S cleavage. These play pivotal role enabling variety valuable formations. Perspective, we highlight advances EDA-complex-mediated involving mechanisms, substrate scope, limitations For sake brevity, article organized into five main sections: (1) Nitrogen-based donor reactions, (2) Oxygen-based (3) Sulfur-based (4) Phosphorus-based (5) π-based focus on C-C, C-S, C-B C-P

Language: Английский

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Synthesis of Sulfoxides by Palladium-Catalyzed Arylation of Sulfenate Anions with Aryl Thianthrenium Salts

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13319 - 13328

Published: Sept. 3, 2024

A novel and highly efficient Pd-catalyzed arylation of sulfenate anions with aryl thianthrenium salts is demonstrated. This procedure provides a practical protocol to synthesize various diaryl alkyl sulfoxides in moderate-to-good yields. The new approach shows mild reaction conditions, broad substrate scope, good functional group tolerance.

Language: Английский

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Pyrrolylsulfonium salts: stable, accessible and versatile pseudohalides for Stille couplings

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Pyrroles functionalised with a thianthrenium or diphenylsulfonium group undergo Stille couplings aryl alkynyl stannanes in good yields, avoiding the issues of instability that can hamper use analogous pyrrolyl halides.

Language: Английский

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