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

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(12), С. 3333 - 3340

Опубликована: Янв. 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.

Язык: Английский

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Direct C(sp3)-H functionalization with aryl and alkyl radicals as intermolecular hydrogen atom transfer (HAT) agents

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Recent years have witnessed the emergence of direct intermolecular C(sp

Язык: Английский

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Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)

Опубликована: Май 7, 2024

Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.

Язык: Английский

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Visible Light/Copper Catalysis-Enabled Arylation and Alkenylation of Phosphorothioates via Site-Selective C–H Thianthrenation

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

An efficient visible light/copper-enabled arylation and alkenylation of phosphorothioates with thianthrenium salts via a C(sp

Язык: Английский

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Palladium-Catalyzed Hiyama-Type Coupling of Thianthrenium and Phenoxathiinium Salts

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6681 - 6686

Опубликована: Июль 26, 2024

Here, we demonstrate palladium-catalyzed Hiyama-type cross-coupling reactions of aryl thianthrenium or phenoxathiinium salts. By employing stable and inexpensive organosilanes, the arylation, alkenylation, alkynylation were realized in high efficiency using commercially available Pd(tBu3P)2 as catalyst, thus providing a reliable method for preparation biaryls, styrenes, acetylenes with broad functional group tolerance under mild conditions. Given accessibility salts from simple arenes remarkable regioselective fashion, this protocol also provides an attractive approach late-stage modification complex bioactive scaffolds.

Язык: Английский

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Pd/NBE-Catalyzed One-Pot Modular Synthesis of Polycyclic Fused δ-Lactams and Investigation of Room-Temperature Phosphorescence

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12181 - 12191

Опубликована: Июль 30, 2024

The advancement of sophisticated synthetic methodologies that streamline reaction processes while enhancing molecular complexity is a perpetual necessity in the realm chemistry. Catalytic one-pot cascade play crucial role efficient construction intricate molecules with exceptional chemoselectivity. Herein, we present approach for synthesis polycyclic fused δ-lactams via sequential phosgenation, Pd/NBE-catalyzed ortho-carbamoylation/ipso-Heck-type cyclization, and C–H activation from readily available aryl halides, amines, triphosgenes. This stands out as first example situ carbamoyl chloride formation amine precursors, presenting an alternative to existing transformations involving chlorides. practical significance these showcased by 81 rapid economically favorable manner, without need intermediate purification. Moreover, were scalable compatible various natural products pharmaceuticals, further underscoring effectiveness this strategy. relatively rigid coplanar structure displayed our synthesized exhibits distinct room-temperature phosphorescence characteristics, which have been utilized anticounterfeiting high-security-level data encryption.

Язык: Английский

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Enabling Aryl Chloride‐Mediated Palladium/Norbornene Cooperative Catalysis

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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Enabling Aryl Chloride‐Mediated Palladium/Norbornene Cooperative Catalysis

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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Pd/NBE-Catalyzed One-Pot Modular Synthesis of Tetrahydro-γ-carbolines

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Tetrahydro-γ-carbolines are especially outstanding fused heterocyclic ring systems possessing significant biological activities in the central nervous system. Here, using commercially available NBE derivatives (NBEs), we report an efficient protocol for one-pot modular synthesis of 4-substituted tetrahydro-γ-carbolines via Catellani/aza-Michael addition cascade from easily 3-iodo-1-tosyl-1H-indole, aziridines and olefins. This approach exhibits a wide substrate scope, good yields, scalability, potential extension toward Mebhydroline analogues.

Язык: Английский

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Palladium-catalyzed carbene C–H insertion reaction of non-activated arenes

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111225 - 111225

Опубликована: Апрель 1, 2025

Язык: Английский

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