A dual light-driven palladium catalyst: Breaking the barriers in carbonylation reactions

Science, Год журнала: 2020, Номер 368(6488), С. 318 - 323

Опубликована: Апрель 16, 2020

Lighting the way coming and going Catalysts accelerate chemical reactions by breaking existing bonds then forming new ones. Often, factors that favor first process can muddle second one, constraining a catalyst's generality. Torres et al. found visible light excitation of palladium complex facilitate both making carbon-halogen (see Perspective Kathe Fleischer). The reaction specifically forms acid chlorides carbonylation wide variety alkyl or aryl bromides iodides. These products in turn react further to form amides esters. Science , this issue p. 318 ; see also 242

Язык: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(22), С. 12313 - 12370

Опубликована: Ноя. 9, 2023

Late-stage functionalization (LSF) introduces functional group or structural modification at the final stage of synthesis natural products, drugs, and complex compounds. It is anticipated that late-stage would improve drug discovery's effectiveness efficiency hasten creation various chemical libraries. Consequently, products a productive technique to produce product derivatives, which significantly impacts biology development. Carbon-carbon bonds make up fundamental framework organic molecules. Compared with carbon-carbon bond construction, activation can directly enable molecular editing (deletion, insertion, atoms groups atoms) provide more efficient accurate synthetic strategy. However, selective unstrained still one most challenging projects in synthesis. This review encompasses strategies employed recent years for cleavage by explicitly focusing on their applicability functionalization. expands current discourse reactions providing comprehensive overview types bonds. includes C-C(sp), C-C(sp2), C-C(sp3) single bonds; double triple bonds, focus catalysis transition metals organocatalysts. Additionally, specific topics, such as ring-opening processes involving three-, four-, five-, six-membered rings, are discussed, exemplar applications these techniques showcased context bioactive molecules discovery. aims shed light advancements field propose potential avenues future research realm

Язык: Английский

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Catalytic Isofunctional Reactions—Expanding the Repertoire of Shuttle and Metathesis Reactions

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(30), С. 10074 - 10103

Опубликована: Сен. 7, 2018

Transfer hydrogenation, alkene metathesis, and alkyne metathesis possess great value to the synthetic chemistry community. One of key features these processes is their reversibility, which can be attributed presence same number type functional groups in both reactants products, making reactions isofunctional. These classic have recently inspired development novel shuttle that offer promise for chemistry. This Review describes systematically categorizes recent older examples other than transfer hydrogenation alkene/alkyne metathesis.

Язык: Английский

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Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(51), С. 16871 - 16876

Опубликована: Окт. 24, 2018

Abstract Methods for the direct synthesis of difluoromethylated arenes are sparse, despite importance difluoromethyl group in medical, agro‐, and materials chemistry. A palladium‐catalyzed decarbonylative cross‐coupling reaction acid chlorides with a zinc reagent is achieved to access compounds. The transformation proceeds at room temperature shows broad functional tolerance, thus providing general efficient method difluoromethylation wide range aromatic carboxylic acids.

Язык: Английский

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The emergence of Pd-mediated reversible oxidative addition in cross coupling, carbohalogenation and carbonylation reactions

Nature Catalysis, Год журнала: 2019, Номер 2(10), С. 843 - 851

Опубликована: Окт. 7, 2019

Язык: Английский

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Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(10), С. 3723 - 3728

Опубликована: Март 3, 2021

We describe a new functional group metathesis between aryl nitriles and thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good excellent yields. Furthermore, the cyanide- thiol-free reaction shows high tolerance great efficiency for late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility utility multistep synthesis.

Язык: Английский

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Palladium‐Catalyzed Asymmetric Markovnikov Hydroxycarbonylation and Hydroalkoxycarbonylation of Vinyl Arenes: Synthesis of 2‐Arylpropanoic Acids

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(43), С. 23117 - 23122

Опубликована: Июль 9, 2021

Abstract Asymmetric hydroxycarbonylation is one of the most fundamental yet challenging methods for synthesis carboxylic acids. Herein, we reported development a palladium‐catalyzed highly enantioselective Markovnikov vinyl arenes with CO and water. A monodentate phosphoramidite ligand L6 plays vital role in reaction. The reaction tolerates range functional groups, provides facile atom‐economical approach to an array 2‐arylpropanoic acids including several commonly used non‐steroidal anti‐inflammatory drugs. catalytic system has also enabled asymmetric hydroalkoxycarbonylation alcohols afford 2‐arylpropanates. Mechanistic investigations suggested that hydropalladation irreversible regio‐ enantiodetermining step, while hydrolysis/alcoholysis probably rate‐limiting step.

Язык: Английский

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Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(27), С. 10333 - 10340

Опубликована: Июнь 28, 2021

A Ni-catalyzed aryl sulfide synthesis through an exchange reaction between sulfides and a variety of electrophiles was developed. By using 2-pyridyl as donor, this achieved the without odorous toxic thiols. The use Ni/dcypt catalyst capable cleaving forming aryl–S bonds important for electrophiles, which include aromatic esters, arenol derivatives, halides. Mechanistic studies revealed that can simultaneously undergo oxidative additions followed by ligand generated aryl–Ni–SR aryl–Ni–OAr species to furnish exchanged compounds.

Язык: Английский

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Versatile Palladium-Catalyzed Approach to Acyl Fluorides and Carbonylations by Combining Visible Light- and Ligand-Driven Operations

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(21), С. 9413 - 9420

Опубликована: Май 19, 2022

We describe the development of a general palladium-catalyzed carbonylative method to synthesize acyl fluorides from aryl, heteroaryl, alkyl, and functionalized organic halides. Mechanistic analysis suggests that reaction proceeds via synergistic combination visible light photoexcitation Pd(0) induce oxidative addition with ligand-favored reductive elimination. These together create unidirectional catalytic cycle is uninhibited by classical effect carbon monoxide coordination. Coupling formation their subsequent nucleophilic reactions has opened perform carbonylation unprecedented breadth, including assembly highly carbonyl-containing products.

Язык: Английский

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Mechanistic Investigation of the Nickel-Catalyzed Metathesis between Aryl Thioethers and Aryl Nitriles

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(29), С. 13096 - 13108

Опубликована: Июль 14, 2022

Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. However, no complete mechanistic studies of these reactions have been reported to date, particularly regarding the nature key functional transfer mechanism. Unraveling mechanism transformations would not only allow for their further improvement but also lead design novel reactions. Herein, we describe our detailed nickel-catalyzed reaction between aryl methyl sulfides and nitriles, combining experimental computational results. These did support a proceeding through reversible migratory insertion nitrile into Ni–Ar bond provided strong alternative involving transmetalation step two independently generated oxidative addition complexes. Extensive kinetic analysis, including rate law determination Eyring indicated complex as resting state catalytic reaction. Depending on concentration sulfide, either reductive elimination or C(sp2)–S sulfide turnover-limiting NMR studies, unusual 31P–2H HMBC experiment using deuterium-labeled complexes, unambiguously demonstrated that cyanide groups exchange during step, rather than moieties. In addition, Hammett analyses Ni(II) complexes revealed this central proceeds via associative Organometallic synthesis, isolation, characterization all putative intermediates possible deactivation shed light mechanism, identification pathway, which has led improved protocol.

Язык: Английский

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