Cross-coupling of aromatic esters and amides

Chemical Society Reviews, Год журнала: 2017, Номер 46(19), С. 5864 - 5888

Опубликована: Янв. 1, 2017

This review highlights the progress in transition-metal-catalyzed decarbonylative and non-decarbonylative cross-coupling of aromatic esters amides.

Язык: Английский

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Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

Organometallics, Год журнала: 2018, Номер 38(1), С. 3 - 35

Опубликована: Ноя. 27, 2018

Cross-coupling reactions, which were discovered almost 50 years ago, are widely used in both industry and academia. Even though cross-coupling reactions now represent mature technology, there is still a significant amount of research this area that aims to improve the scope these develop more efficient catalysts, make practical. In tutorial, brief background provided, then major advances over last 20 described. These include development improved ligands precatalysts for extension much wider range electrophiles. For example, common with sp3-hybridized electrophiles as well ester, amide, ether, aziridine substrates. many modern substrates, traditional palladium-based catalysts less than systems based on first-row transition metals such nickel. Conventional have also inspired related cross-electrophile decarboxylative couplings metallaphotoredox chemistry. The new probably at same stage 30 tutorial highlights how strategies may be applicable making

Язык: Английский

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The Suzuki-Miyaura reaction after the Nobel prize

Coordination Chemistry Reviews, Год журнала: 2019, Номер 385, С. 137 - 173

Опубликована: Фев. 13, 2019

Язык: Английский

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Well-Defined Palladium(II)–NHC Precatalysts for Cross-Coupling Reactions of Amides and Esters by Selective N–C/O–C Cleavage

Accounts of Chemical Research, Год журнала: 2018, Номер 51(10), С. 2589 - 2599

Опубликована: Сен. 21, 2018

Transition-metal-catalyzed cross-coupling reactions represent a most powerful tool for the rapid construction of C-C and C-X bonds available to synthetic chemists. Recently, tremendous progress has been made in burgeoning area amides esters enabled by regio- chemoselective acyl (X = N, O) cleavage using well-defined Pd(II)-NHC complexes. The use N-heterocyclic carbenes as ligands palladium-catalyzed cross-couplings permits that were previously impossible palladium or could be achieved only under harsh conditions. These provide an attractive method chemists manipulate traditionally inert amide ester with broad generality inherent catalysis. Research stable electrophiles can broadly categorized type electrophile undergoing cross-coupling. Recent studies have shown transition-metal catalysis represents one straightforward wide-ranging ways manipulating classically into generic acyl-metal intermediates systematically exploited new paradigm organic synthesis. key achieving high chemoselectivity process is control amidic resonance (nN πC═O* conjugation, rotation ca. 15-20 kcal/mol planar amides), enabling oxidative addition N-C bond metal rational predictable manner. This mode extended C(acyl)-O aryl esters, where selective C-O accomplished through match nucleophilic catalysts. two types transition-metal-catalyzed concept chemistry because ubiquity precursors Furthermore, stability provides unprecedented opportunities orthogonal strategies presence other electrophiles. In this Account, we highlight advances taken place past few years field focusing on both (1) stereoelectronic properties complexes critical realize challenging manifold (2) role isomerization barrier broader sense, described here practical approach functionalize common functional groups synthesis establishes access enable nonconventional strategies.

Язык: Английский

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A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes

Nature Communications, Год журнала: 2018, Номер 9(1)

Опубликована: Авг. 23, 2018

Abstract The construction of an aryl ketone structural unit by means catalytic carbon–carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved direct deoxygenative synthesis aqueous solution from readily available aromatic carboxylic acids and alkenes, affording structurally diverse ketones moderate to good yields. Visible-light photoredox catalysis enables deoxygenation as acyl sources with triphenylphosphine a distinct perspective on activation. synthetic robustness is supported late-stage modification several pharmaceutical compounds complex molecules. This strategy further applied drug zolpidem three steps 50% total yield concise cyclophane-braced 18–20 membered macrocycloketones. It not only advancement for streamlined feedstock chemicals, but also radical activation mode beyond redox potential acids.

Язык: Английский

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Highly Chemoselective, Transition-Metal-Free Transamidation of Unactivated Amides and Direct Amidation of Alkyl Esters by N–C/O–C Cleavage

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(28), С. 11161 - 11172

Опубликована: Июнь 16, 2019

The amide bond is one of the most fundamental functional groups in chemistry and biology plays a central role numerous processes harnessed to streamline synthesis key pharmaceutical industrial molecules. Although amides frequently performed reactions by academic scientists, direct transamidation tertiary challenging due unfavorable kinetic thermodynamic contributions process. Herein, we report first general, mild, highly chemoselective method for unactivated acyl N–C cleavage with non-nucleophilic amines. This operationally simple absence transition metals operates under unusually mild reaction conditions. In this context, further describe amidation abundant alkyl esters afford bonds exquisite selectivity C–O cleavage. utility process showcased broad scope method, including various sensitive groups, late-stage modification, drug molecules (>80 examples). Remarkable toward different within ester electrophiles that not feasible using existing methods was observed. Extensive experimental computational studies were conducted provide insight into mechanism origins high selectivity. We present series guidelines predict reactivity valuable user-friendly light importance organic major practical advantages study opens up new opportunities pivotal range chemical contexts.

Язык: Английский

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Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules

Accounts of Chemical Research, Год журнала: 2018, Номер 51(5), С. 1185 - 1195

Опубликована: Апрель 13, 2018

ConspectusThe utilization of carboxylic acid esters as electrophiles in metal-catalyzed cross-coupling reactions is increasingly popular, environmentally friendly and readily available ester derivatives can be powerful alternatives to the commonly used organohalides. However, key challenges associated with use these chemicals remain addressed, including stability substrates high energy barrier their oxidative addition low-valent metal species. Due recent developments nickel catalysis that make it easier perform additions, chemists have become interested applying less reactive coupling counterparts nickel-catalyzed transformations. Hence, our group others independently investigated various substitutions functionalizations enabled by catalysis. Such methods are great interest they enable exchange groups, which directing groups C–H prior replacement.Here, we summarize efforts toward development decarbonylative esters. Achievements accomplished other this area also included. To day, a number new transformations been successfully developed, arylations, alkylations, cyanations, silylations, borylations, aminations, thioetherifications, stannylations, hydrogenolysis reactions. These proceed via pathway shown degree reactivity chemoselectivity, well several unique advantages terms substrate availability, due partners.Although mechanisms not yet fully understood, already provided some important insights. For example, Yamamoto explored stoichiometric nickel-mediated decarbonylation process proposed reaction mechanism involving C(acyl)–O bond cleavage CO extrusion. Key intermediates were isolated characterized Shi co-workers, supporting assumption nickel/N-heterocyclic carbene-promoted activation functionalization. Our combined experimental computational study ligand-controlled chemoselective aromatic alkylboron reagents further insight into mechanism.We demonstrated complexes bidentate ligands favor C(aryl)–C step, resulting while monodentate phosphorus promote bond, leading production ketone products. Although more detailed mechanistic investigations need undertaken, successful serve solid foundation for future studies.We believe type will significant value, particularly combination retrosynthetic analysis synthesis natural products biologically active molecules. Thus, presented substitution pave way applications construction complex frameworks late-stage modification functionalization derivatives.

Язык: Английский

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Highly selective transition-metal-free transamidation of amides and amidation of esters at room temperature

Nature Communications, Год журнала: 2018, Номер 9(1)

Опубликована: Окт. 3, 2018

Abstract Amide chemistry has an essential role in the synthesis of high value molecules, such as pharmaceuticals, natural products, and fine chemicals. Over past years, several examples transamidation reactions have been reported. In general, transition-metal-based catalysts or harsh conditions are employed for these transformations due to unfavorable kinetics thermodynamics process. Herein, we report a significant advance this area present general method transition-metal-free amides amidation esters by highly selective acyl cleavage with non-nucleophilic amines at room temperature. contrast metal-catalyzed protocols, is operationally-simple, environmentally-friendly, operates under exceedingly mild conditions. The practical highlighted valuable yields. Considering key various branches chemical science, envision that broadly applicable will be great interest organic synthesis, drug discovery, biochemistry.

Язык: Английский

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Mechanistic Aspects of the Palladium‐Catalyzed Suzuki‐Miyaura Cross‐Coupling Reaction

Chemistry - A European Journal, Год журнала: 2021, Номер 27(54), С. 13481 - 13493

Опубликована: Июль 16, 2021

The story of C-C bond formation includes several reactions, and surely Suzuki-Miyaura is among the most outstanding ones. Herein, a brief historical overview insights regarding reaction mechanism provided. In particular, catalytically active species probably main concern, thus preactivation in competition with, or even assumes role rate determining step (rds) overall reaction. Computational chemistry key identifying rds leading to milder conditions on an experimental level by means predictive catalysis.

Язык: Английский

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Recent Advances in Acyl Suzuki Cross-Coupling

Catalysts, Год журнала: 2019, Номер 9(1), С. 53 - 53

Опубликована: Янв. 8, 2019

Acyl Suzuki cross-coupling involves the coupling of an organoboron reagent with acyl electrophile (acyl halide, anhydride, ester, amide). This review provides a timely overview very important advances that have recently taken place in acylative cross-coupling. Particular emphasis is directed toward type electrophiles, catalyst systems and new partners. will be value to synthetic chemists involved this rapidly developing field as well those interested using for synthesis ketones catalytic alternative stoichiometric nucleophilic additions or Friedel-Crafts reactions.

Язык: Английский

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