Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Язык: Английский

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One-Pot Synthesis of Sulfonamides from Unactivated Acids and Amines via Aromatic Decarboxylative Halosulfonylation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(39), С. 21189 - 21196

Опубликована: Сен. 20, 2023

The coupling of carboxylic acids and amines to form amide linkages is the most commonly performed reaction in pharmaceutical industry. Herein, we report a new strategy that merges these traditional partners generate sulfonamides, important bioisosteres. This method leverages copper ligand-to-metal charge transfer (LMCT) convert aromatic sulfonyl chlorides, followed by one-pot amination corresponding sulfonamide. process requires no prefunctionalization native acid or amine extends diverse set aryl, heteroaryl, s-rich aliphatic substrates. Further, extend this synthesis (hetero)aryl fluorides, which have found utility as "click" handles chemical probes programmable bifunctional reagents. Finally, demonstrate protocols analogue synthesis.

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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Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10930 - 10937

Опубликована: Май 15, 2023

Amines and carboxylic acids are abundant synthetic building blocks that classically united to form an amide bond. To access new pockets of chemical space, we interested in the development amine-acid coupling reactions complement coupling. In particular, formation carbon-carbon bonds by formal deamination decarboxylation would be impactful addition synthesis toolbox. Here, report a cross-coupling alkyl amines aryl C(sp

Язык: Английский

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Skeletal metalation of lactams through a carbonyl-to-nickel-exchange logic

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 29, 2023

Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending logic metal-carbon would enable direct modification of carbon frameworks with new implications retrosynthetic analysis. However, transformation requires selective cleavage highly inert chemical and formation stable intermediates amenable further synthetic elaborations, hence its development has remained considerably challenging. Here we introduce skeletal strategy that allows lactams, prevalent motif bioactive molecules, be readily converted into well-defined, synthetically useful organonickel reagents. The reaction features activation unstrained amide C-N mediated by an easily prepared Ni(0) reagent, followed CO deinsertion dissociation under mild room temperature conditions formal carbonyl-to-nickel-exchange process. underlying principles this unique reactivity are rationalized organometallic computational studies. is applied excision isotope underscoring potential synthesis.

Язык: Английский

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A decarbonylative approach to alkylnickel intermediates and C(sp ³ )-C(sp ³ ) bond formation

Science, Год журнала: 2024, Номер 385(6715), С. 1331 - 1337

Опубликована: Сен. 19, 2024

The myriad nickel-catalyzed cross-coupling reactions rely on the formation of an organonickel intermediate, but limitations in forming monoalkylnickel species have limited options for C(sp 3 ) cross-coupling. monoalkylnickel(II) from abundant carboxylic acid esters would be valuable, derivatives are primarily decarboxylated to form alkyl radicals that lack correct reactivity. In this work, we disclose a facile oxidative addition and decarbonylation sequence forms intermediates through nonradical process. key ligand, bis(4-methylpyrazole)pyridine, accelerates decarbonylation, stabilizes alkylnickel(II) destabilizes off-cycle nickel(0) carbonyl species. utility new reactivity )-C(sp bond is demonstrated reaction challenging by purely radical methods—the selective primary with iodides.

Язык: Английский

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Nickel‐Catalyzed Cross‐Electrophile Coupling of Triazine Esters with Aryl Bromides

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(24), С. 3539 - 3546

Опубликована: Авг. 19, 2023

Comprehensive Summary Cross‐electrophile coupling of triazine esters with aryl bromides could be facilely accomplished by employing nickel as catalyst, magnesium metal mediator, and lithium chloride additive. The reactions proceeded efficiently in THF at room temperature through C—O bond activation to afford an array structurally different diaryl ketones moderate good yields wide functional group tolerance. Control experiments showed that nickel, magnesium, chloride, are all indispensable for the performance reaction. Preliminary mechanistic exploration indicated situ formed arylmagnesium reagent insertion into bromide might serve key intermediate cross‐coupling. method which avoids utilization moisture‐labile relatively difficult‐to‐obtain organometallics is step‐economical, cost‐efficient, operationally simple, potentially serving attractive alternative documented methods.

Язык: Английский

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Persistent organonickel complexes as general platforms for Csp2–Csp3 coupling reactions

Nature Chemistry, Год журнала: 2024, Номер 16(9), С. 1515 - 1522

Опубликована: Апрель 29, 2024

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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Anhydrous and Stereoretentive Fluoride-Enhanced Suzuki–Miyaura Coupling of Immunomodulatory Imide Drug Derivatives

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 4595 - 4606

Опубликована: Март 7, 2024

Immunomodulatory imide drugs form the core of many pharmaceutically relevant structures, but Csp2–Csp2 bond formation via metal-catalyzed cross coupling is difficult due to sensitivity glutarimide ring ubiquitous in these structures. We report that replacement traditional alkali base with a fluoride source enhances previously challenging Suzuki–Miyaura on glutarimide-containing compounds trifluoroborates. These enabling conditions are reactive enough generate derivatives high yields mild preserve both and its sensitive stereocenter. Experimental computational data suggest mechanistically distinct process π-coordination trifluoroborate enabled by conditions.

Язык: Английский

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