Multimetallic-Catalyzed C–C Bond-Forming Reactions: From Serendipity to Strategy

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6596 - 6614

Опубликована: Март 13, 2023

The use of two or more metal catalysts in a reaction is powerful synthetic strategy to access complex targets efficiently and selectively from simple starting materials. While capable uniting distinct reactivities, the principles governing multimetallic catalysis are not always intuitive, making discovery optimization new reactions challenging. Here, we outline our perspective on design elements using precedent well-documented C–C bond-forming reactions. These strategies provide insight into synergy compatibility individual components reaction. Advantages limitations discussed promote further development field.

Язык: Английский

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Radical Covalent Catalysis: Recent Advances and Future Developments

ChemCatChem, Год журнала: 2023, Номер 15(14)

Опубликована: Июнь 14, 2023

Abstract Radical covalent catalysis, namely radical catalysis via a catalyst addition and elimination process, has emerged in the past few decades. This review is aimed to summarize recent advances of by highlighting some outstanding challenges confirming potential areas improvement, which may offer inspiration for future studies.

Язык: Английский

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Versatile Direct (Hetero)Arylation Polymerization of Electro‐Deficient Unsubstituted Thiazolo[5,4‐d]Thiazole: A Tool to Lower the LUMO Level

Macromolecular Rapid Communications, Год журнала: 2025, Номер unknown

Опубликована: Май 13, 2025

Abstract A series of novel conjugated semiconducting polymers based on the unsubstituted thiazolo[5,4‐ d ]thiazole (TzTz) unit is synthesized using atom‐economic and environmentally friendly direct (hetero)arylation polymerization (DHAP). The versatility proposed conditions, employing a non‐chlorinated moderately toxic solvent cooperative palladium/copper bimetallic catalytic system, demonstrated through use seven comonomers with varying electron‐withdrawing strength: 2,2′‐bithiophene (BT), 6,7‐difluoroquinoxaline (Qx), thieno[3,4‐ c ]pyrrole‐4,6(5H)‐dione (TPD), 5,6‐difluorobenzo[ ][1,2,5]thiadiazole (BTD), isoindigo (IID), para‐azaquinodimethane (AQM) 2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione (DPP). resulting TzTz‐based copolymers exhibit optical bandgaps between 1.5 2.0 eV HOMO/LUMO energy levels spanning from −5.2/−3.3 to −5.4/−3.9 eV. They all show satisfactory thermal stability for electronic applications (Td = 300−360 °C). Notably, are observed they generally improved backbone planarity deeper LUMO than their thiophene derivatives. synthesis tool finely lower next‐generation A‐A’ in view increasing performance air‐stability doped organic electronics believed be provided by this work.

Язык: Английский

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Cascade C─H‐Alkenylation‐Intramolecular Aminative Cyclization of Benzylsulfonamides for Synthesis of Isoindoline Cores

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

Опубликована: Май 21, 2025

Abstract Several isoindoline‐core‐bearing compounds are pharmaceutically relevant due to their activity against a myriad of diseases. Traditionally, the isoindoline core is synthesized from benzylamines by two‐step synthesis involving ortho ‐C─H alkenylation followed acid‐ or metal‐catalyzed cyclization. In this study, we execute direct one‐step procedure alkenylation‐oxidative intramolecular aminative cyclization pyridinesulfonamide derivatives with different acrylates and vinyl sulfones using Pd(II)‐salt as catalyst, Ag(I)‐salt additive, Cu(II)‐salt oxidant. The reactions tolerant several functional groups on benzylamine well alkyl acrylates, providing products moderate excellent yields. Control experiments computational studies revealed importance pyridine‐3‐sulfonamide for reaction since it provides key site stabilizing an intermediate species which favors C─H activation oxidative amination‐based process.

Язык: Английский

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Acetoxy Group-Directed Regioselective C2 Alkenylation of Indoles via Pd–Ag Bimetallic Catalysis

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(20), С. 14423 - 14434

Опубликована: Окт. 5, 2023

Regioselective C–H functionalizations of indoles reported to date with directing groups at C3 mainly rely on functional that are linked the indole via C–C bonds. However, core by C–X linkages also attractive due possibility further modifications bond. Herein, we report a 3-acetoxy group for regioselective C2 alkenylation activation-based, cross-dehydrogenative, oxidative Heck-type reaction. The reaction is catalyzed Pd(II) and Ag(I) stoichiometric Cu(II) as oxidant provides 2-alkenylated in yields 52–84%. conditions compatible several different positions well N-protecting or free NH core. With respect alkene coupling partners, reactions successful acrylates, vinyl sulfates, phosphates. Specifically designed experiments, density theory (DFT) computational studies, reveal heterodinuclear [Pd(μ-OAc)3Ag] bimetallic species actual catalyst responsible alkenylation. A mechanistic path involving this catalytic was found be favorable over other possible pathways explaining observed regioselectivity through DFT studies.

Язык: Английский

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Multi-functional photocatalytic systems for solar fuel production

Journal of Materials Chemistry A, Год журнала: 2023, Номер 11(27), С. 14614 - 14629

Опубликована: Янв. 1, 2023

This review focuses on multi-functional photocatalytic systems for solar fuel production by combining water oxidation and proton or CO 2 reduction to pave a new way produce fuels more effectively than natural photosynthesis.

Язык: Английский

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Ru‐, Rh‐ and Ir‐Catalyzed Enantioselective sp³C−H Functionalization

Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(24)

Опубликована: Окт. 22, 2022

Abstract The development of novel methodologies that enable the construction complex chiral molecular scaffolds in an atom and step‐economic manner has always been area immense interest significant synthetic value. transition metal‐catalyzed enantioselective sp 3 C−H activation functionalization reactions serve as expeditious means for introducing diverse functionalities a straightforward manner. However, controlling chemo‐ stereoselectivity these is challenge owing to their ubiquity low reactivity. In this review, we present comprehensive account on recent advances inter‐ intramolecular asymmetric bond utilizing ruthenium, rhodium, iridium catalysts get insights into mechanistic aspects transformations.

Язык: Английский

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CuX Dual Catalysis: Construction of Oxazolo[2,3-b][1,3]oxazines via a Tandem CuAAC/Ring Cleavage/[4+2+3] Annulation Reaction

Organic Letters, Год журнала: 2022, Номер 24(40), С. 7300 - 7304

Опубликована: Сен. 30, 2022

CuX as a simple dual catalyst strategy that promotes the tandem transformations of fused oxazolo[2,3-b][1,3]oxazines has been developed. Copper catalyzed terminal ynones, sulfonyl azides, and nitriles for CuAAC/ring cleavage/[4+2] annulation reaction, while halogen ring cleavage [2+3] oxiranes to form final products. This study provides four-component, one-pot synthesizing complex heterocycles from ingredients expands application CuAAC in organic synthesis.

Язык: Английский

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Palladium-Catalyzed Annulation of Tertiary Anilines with 3-Butenoic Acid via Dual C–H Bond Activation

Organic Letters, Год журнала: 2024, Номер 26(21), С. 4422 - 4426

Опубликована: Май 20, 2024

Catalytic cyclization via dual C-H bond activation has evolved as a powerful strategy for building bi- and polycyclic molecules. Herein, palladium-catalyzed annulation of tertiary anilines with 3-butenoic acid

Язык: Английский

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Direct Regioselective Hydro(hetero)arylation/Cyclocondensation Reactions of β-(2-Aminophenyl)-α,β-ynones by Means of Transition-Metal Catalysis/Brønsted Acid Synergism: Experimental Results and Computational Insights

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(11), С. 6857 - 6867

Опубликована: Май 10, 2023

Experimental results and computational insights explain the key role of transition-metal catalysis/Brønsted acid synergism in achievement sequential regioselective direct heteroarylation/cyclocondensation reactions β-(2-aminophenyl)-α,β-ynones with a variety electron-rich aromatic heterocyclic/arenes to afford quinoline-(hetero)aromatic hybrids. The first approach synthesis 4-(1H-pyrrol-2-yl)quinolines is described. effectiveness various transition metals compared.

Язык: Английский

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