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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Formation of C(sp²)–C(sp³) Bonds Instead of Amide C–N Bonds from Carboxylic Acid and Amine Substrate Pools by Decarbonylative Cross-Electrophile Coupling

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 9951 - 9958

Опубликована: Май 1, 2023

Carbon-heteroatom bonds, most often amide and ester are the standard method to link together two complex fragments because carboxylic acids, amines, alcohols ubiquitous reactions reliable. However, C-N C-O linkages a metabolic liability they prone hydrolysis. While C(sp

Язык: Английский

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Divergent Acyl and Decarbonylative Liebeskind–Srogl Cross-Coupling of Thioesters by Cu-Cofactor and Pd–NHC (NHC = N-Heterocyclic Carbene) Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 1848 - 1855

Опубликована: Янв. 17, 2023

Transition-metal-catalyzed cross-coupling reactions of thioesters by selective acyl C(O)–S cleavage have emerged as a powerful platform for the preparation complex molecules. Herein, we report divergent Liebeskind–Srogl Pd–NHC (NHC = N-heterocyclic carbene) catalysis. The reaction provides straightforward access to functionalized ketones highly C(acyl)–S under mild conditions. Most crucially, conditions enable direct functionalization range pharmaceuticals decorated with palette sensitive functional groups, providing attractive products medicinal chemistry programs. Furthermore, decarbonylative C(acyl)–S/C(aryl)–C(O) is reported. Cu metal cofactor directs pathway an or pathway. This reactivity applicable pharmaceuticals. represents mildest Suzuki discovered date. Cu-directed and opens up chemical space in molecule synthesis.

Язык: Английский

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Stereospecific Acylative Suzuki–Miyaura Cross-Coupling: General Access to Optically Active α-Aryl Carbonyl Compounds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7075 - 7083

Опубликована: Март 2, 2023

A novel strategy for the stereospecific Pd-catalyzed acylative cross-coupling of enantiomerically enriched alkylboron compounds has been developed. The protocol features an extremely high level enantiospecificity to allow facile access synthetically challenging and valuable chiral ketones carboxylic acid derivatives. use a sterically encumbered electron-rich phosphine ligand proved be crucial success reaction. Furthermore, on basis experimental computational studies, unique mechanism transmetalation, assisted by noncovalent interactions C(sp3)-based organoboron reagent, identified.

Язык: Английский

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Ligand Relay for Nickel‐Catalyzed Decarbonylative Alkylation of Aroyl Chlorides

Advanced Science, Год журнала: 2023, Номер 11(9)

Опубликована: Дек. 13, 2023

Abstract Transition metal‐catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late‐stage applications. The development selective decarbonylative acid derivatives, most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable meaningful, but remains challenging. Herein, a strategy nickel‐catalyzed alkylation chlorides via phosphine/nitrogen ligand relay reported. simple phosphine found essential decarbonylation step, while nitrogen promotes cross‐electrophile coupling. Such system can effectively orderly carry out catalytic process at room temperature, utilizing easily available as an aryl electrophile reductive alkylation. This discovery provides new coupling, features operationally simple, conditions, excellent functional group tolerance. approach applied to methylation various pharmaceuticals. Extensive experiments are carried provide insights into reaction pathway support process.

Язык: Английский

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Palladium‐Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand‐Assisted Halide Exchange

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(31), С. 17211 - 17217

Опубликована: Май 20, 2021

We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive abundant aryl vinyl carboxylic acids via in situ activation to the acid chloride formation a phosphonium salt. The use 1-iodobutane as iodide source combination with base deoxychlorinating reagent gives access wide range iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments kinetic analysis suggest unique mechanism involving C-P reductive elimination form Xantphos chloride, which subsequently initiates unusual halogen exchange by outer sphere nucleophilic substitution.

Язык: Английский

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Recent advances in nickel catalyzed Suzuki-Miyaura cross coupling reaction via C-O& C-N bond activation

Sustainable Chemistry and Pharmacy, Год журнала: 2023, Номер 32, С. 100953 - 100953

Опубликована: Янв. 11, 2023

Язык: Английский

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Cu(ii)-catalyzed ‘in-water’ N-arylation of electron-deficient NH-heterocycles

Green Chemistry, Год журнала: 2024, Номер 26(6), С. 3149 - 3158

Опубликована: Янв. 1, 2024

Cu( ii )-catalyzed robust efficient in-water N -arylation of electron-poor NH-heterocycles is reported. Wide substrate scope, decent yields, functional group tolerance, gram-scale synthesis, synthetic elaboration, late-stage arylation mirror advantages.

Язык: Английский

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Oxime-palladacycle complex supported on magnetic nanoparticles: a recyclable catalyst for Suzuki-type decarbonylative cross-coupling of esters with aryl boronic acid

Catalysis Science & Technology, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A heterogeneous and recyclable bis-oxime palladacycle-derived silica immobilized palladium catalyst for decarbonylative cross-coupling reactions of esters with arylboronic acid in the presence 2-MeTHF.

Язык: Английский

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Synthesis of ortho-arylated and alkenylated benzamides by palladium-catalyzed denitrogenative cross-coupling reactions of 1,2,3-benzotriazin-4(3H)-ones with organoboronic acids

New Journal of Chemistry, Год журнала: 2021, Номер 45(37), С. 17190 - 17195

Опубликована: Янв. 1, 2021

An efficient palladium-catalyzed denitrogenative cross-coupling reaction of 1,2,3-benzotriazin-4(3 H )-ones with organoboronic acids is described. The affords various ortho -aryl and alkenylated benzamides in good to high yields.

Язык: Английский

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