Pd-catalyzed regioselective activation of C(sp²)–H and C(sp³)–H bonds

Chemical Society Reviews, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Differentiating between two highly similar C-H bonds in a given molecule remains fundamental challenge synthetic organic chemistry. Directing group assisted strategies for the functionalisation of proximal has been known last few decades. However, distal bond is strenuous and requires distinctly specialised techniques. In this review, we summarise advancement Pd-catalysed C(sp

Язык: Английский

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Unlocking the Nucleophilicity of Strong Alkyl C–H Bonds via Cu/Cr Catalysis

ACS Central Science, Год журнала: 2023, Номер 9(4), С. 756 - 762

Опубликована: Март 27, 2023

Direct functionalization of inert C-H bonds is one the most attractive yet challenging strategies for constructing molecules in organic chemistry. Herein, we disclose an unprecedented and Earth abundant Cu/Cr catalytic system which unreactive alkyl are transformed into nucleophilic alkyl-Cr(III) species at room temperature, enabling carbonyl addition reactions with strong bonds. Various aryl alcohols furnished under mild reaction conditions even on a gram scale. Moreover, this new radical-to-polar crossover approach further applied to 1,1-difunctionalization aldehydes alkanes different nucleophiles. Mechanistic investigations reveal that aldehyde not only acts as reactant but also serves photosensitizer recycle Cu Cr catalysts.

Язык: Английский

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Recent advances in the design and applications of platinum-based supramolecular architectures and macromolecules

Coordination Chemistry Reviews, Год журнала: 2023, Номер 486, С. 215113 - 215113

Опубликована: Март 27, 2023

Язык: Английский

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Enantioselective Synthesis of 1,2‐Benzothiazine 1‐Imines via Ru^II/Chiral Carboxylic Acid‐Catalyzed C−H Alkylation/Cyclization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(29)

Опубликована: Май 17, 2023

Sulfondiimines are diaza-analogues of sulfones with a chiral sulfur center. Compared to and sulfoximines, their synthesis transformations have so far been studied lesser extent. Here, we report the enantioselective 1,2-benzothiazine 1-imines, i.e., cyclic sulfondiimine derivatives from sulfondiimines sulfoxonium ylides via C-H alkylation/cyclization reactions. The combination [Ru(p-cymene)Cl2 ]2 newly developed spiro carboxylic acid is key achieving high enantioselectivity.

Язык: Английский

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Nickel-Catalyzed Functionalization Reactions Involving C–H Bond Activation via an Amidate-Promoted Strategy and Its Extension to the Activation of C–F, C–O, C–S, and C–CN Bonds

Accounts of Chemical Research, Год журнала: 2023, Номер 56(21), С. 3053 - 3064

Опубликована: Окт. 11, 2023

ConspectusThe development of functionalization reactions involving the activation C-H bonds has evolved extensively due to atom and step economy associated with such reactions. Among these reactions, chelation assistance been shown provide a powerful solution serious issues reactivity regioselectivity faced in bonds. The vast majority reported thus far involved use precious metals. Kleiman Dubeck cyclonickelation azobenzene NiCp2 which an azo group directs Ni center activate ortho bond close proximity. Although this stoichiometric reaction was discovered earlier than that for other transition-metal complexes, its as catalytic delayed. No general systems were available Ni-catalyzed long time. This Account details our group's Ni(0)- Ni(II)-catalyzed chelation-assisted It also highlights how new strategy can be extended unreactive bonds.In early 2010s, we found Ni(0)-catalyzed aromatic amides contain 2-pyridinylmethylamine moiety directing alkynes results C-H/N-H oxidative annulation give isoquinolinones. In addition, combination Ni(II) catalyst 8-aminoquinoline superior developing wide variety various electrophiles. proposed include formation unstable Ni(IV) and/or Ni(III) species; generation high-valence species rare at time, but since then, many papers dealing DFT organometallic studies have appeared literature attempts understand mechanism. Based on in-depth considerations mechanism respect why N,N-bidentate is required, realized N-Ni by addition N-H Ni(0) or ligand exchange between key step. We concluded precoordination N(sp2) positions proximity permits bond. working hypothesis, carried out using KOtBu base do not specific desired isoquinolinone, amidate anion acts actual group. Remarkably, applicable C-F, C-O, C-S, C-CN.

Язык: Английский

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Construction of Si‐Stereogenic Silanols by Palladium‐Catalyzed Enantioselective C−H Alkenylation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Фев. 27, 2024

The construction of silicon-stereogenic silanols via Pd-catalyzed intermolecular C-H alkenylation with the assistance a commercially available L-pyroglutamic acid has been realized for first time. Employing oxime ether as directing group, silanol derivatives could be readily prepared excellent enantioselectivities, featuring broad substrate scope and good functional group tolerance. Moreover, parallel kinetic resolution unsymmetric substrates further highlighted generality this protocol. Mechanistic studies indicate that stabilize Pd catalyst provide chiral induction. Preliminary computational unveil origin enantioselectivity in bond activation step.

Язык: Английский

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Palladium-Catalyzed Intermolecular Functionalization of Unactivated Methylene C(sp³)—H Bonds

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(2), С. 620 - 620

Опубликована: Янв. 1, 2025

Язык: Английский

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Enantioselective β-C(sp³)–H Nucleophilic Tosylation of Native Amides: A Synthetic Platform for Chiral Methyl Stereocenters

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 31, 2025

Enantioselective oxygenation of unactivated C(sp3)-H bonds via asymmetric metalation remains an unsolved challenge. Herein we report the development a Pd-catalyzed, enantioselective tosylation native amides with NaOTs as nucleophile, representing rare example C-H functionalization nucleophilic coupling partner. High enantioselectivity in this reaction is achieved by chiral monoprotected amino sulfonamide (MPASA) ligands. Substantial enhancement silver salt additives was also observed. Through desymmetrization readily available isopropyl moiety, structurally diverse β-tosylated bearing α-methyl stereocenter were obtained high yield and enantioselectivity, which complements current enzymatic method for making Roche ester synthon. The tosylated products are highly versatile building blocks further diversifications nitrogen, oxygen, other nucleophiles, thus providing platform constructing methyl stereocenters.

Язык: Английский

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Ligand-Enabled Pd(II)-Catalyzed β-Methylene C(sp³)–H Arylation of Free Aliphatic Acids

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(45), С. 20550 - 20553

Опубликована: Ноя. 7, 2022

Ligand development has enabled rapid advances in Pd(II)-catalyzed β-methyl C(sp3)–H activation of free carboxylic acids. However, there are only a handful reports free-acid-directed β-methylene activation, all which limited to intramolecular reactions. Herein, we report the first intermolecular arylation aliphatic acids, is by bidentate pyridine–pyridone ligands. The bite angle this ligand been discovered play key role promoting C–H acid. This new transformation provides disconnection for alkylation arenes with simple A variety including antiasthmatic drug seratrodast, were compatible reported protocol.

Язык: Английский

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Palladium‐Catalyzed Atroposelective Kinetic C−H Olefination and Allylation for the Synthesis of C−B Axial Chirality

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(47)

Опубликована: Окт. 16, 2023

Abstract The direct C−H functionalization of 1,2‐benzazaborines, especially asymmetric version, remains a great challenge. Here we report palladium‐catalyzed enantioselective olefination and allylation reactions 1,2‐benzazaborines. This approach is kinetic resolution (KR), providing various C−B axially chiral 2‐aryl‐1,2‐benzazaborines 3‐substituted in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). synthetic potential this reaction showcased by late‐stage modification complex molecules, scale‐up reaction, applications.

Язык: Английский

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