Generation and transformation of α-oxy carbene intermediates enabled by copper-catalyzed carbonylation

Green Carbon, Год журнала: 2024, Номер 2(1), С. 70 - 80

Опубликована: Янв. 11, 2024

Since the Fischer-Tropsch reaction was discovered by Otto Roelen in 1938, transition metal-catalyzed carbonylation reactions come as one of most important methods for preparing carbonyl-containing and carbon chain-increased compounds. As a result, field research has received considerable attention over past decades continues to increase. With continuous development in-depth study mechanism, more mechanistic details variations have been revealed, which provide possibilities organic synthesis. Recently, copper catalysis introduced carbonylative functionalization alkenes, thus enabling rapid assembly functionalized carbonyl compounds from simple starting materials. In this Account, we summarize new findings Cu-catalyzed borocarbonylation alkenes based on generation transformation α-oxy carbene intermediates. We believe that results presented Account will further inspire design reactions.

Язык: Английский

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Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(8), С. 4925 - 4941

Опубликована: Янв. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Язык: Английский

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Light-Mediated Synthesis of Aliphatic Anhydrides by Cu-Catalyzed Carbonylation of Alkyl Halides

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(17), С. 9423 - 9427

Опубликована: Апрель 19, 2023

Acid anhydrides are valuable in the chemical industry for their role synthesizing polymers, pharmaceuticals, and other commodities, but syntheses often involve multiple steps with precious metal catalysts. The simplest anhydride, acetic is currently produced by two Rh-catalyzed carbonylation reactions on a bulk scale its use products ranging from aspirin to cellulose acetate. Here, we report light-mediated, Cu-catalyzed process producing aliphatic, symmetric acid directly of alkyl (pseudo)halides single step without any additives. transformation requires only simple Cu salts abundant bases generate heterogeneous Cu0 photocatalyst situ, maintains high efficiency selectivity upon scale-up, operates radical mechanism several beneficial features. This discovery will enable engineering processes commodity efficiently sustainably.

Язык: Английский

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Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 7971 - 7978

Опубликована: Март 14, 2024

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing expedient construction unsymmetric dialkyl ketones broad functional group tolerance. The leverage newly developed

Язык: Английский

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Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies

Green Synthesis and Catalysis, Год журнала: 2024, Номер 5(4), С. 211 - 269

Опубликована: Май 6, 2024

The development of catalytic carbonylation reactions has increased considerably. Although many reviews/chapters/books on have been published, summaries cheap metal-catalyzed aryl halides and other chemical bonds with high dissociation energy C-Y (Y = O, N, H) are still very rare. Focusing green sustainable chemistry, this review summarizes discusses the achievements carbonylative transformations (C(sp2)-X) strong based non-expensive metal catalysts (Co, Mn, Mo, Ni, Fe, Cu), photochemical electrochemical systems developed in recent decades.

Язык: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Год журнала: 2024, Номер 124(17), С. 10192 - 10280

Опубликована: Авг. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Язык: Английский

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Synchronous recognition of amines in oxidative carbonylation toward unsymmetrical ureas

Science, Год журнала: 2024, Номер 386(6723), С. 776 - 782

Опубликована: Ноя. 14, 2024

Unsymmetrical ureas are commonly found in pharmaceuticals and bioactive compounds. However, devising strategies to introduce two distinct amines selectively the construction of unsymmetrical remains a challenge. In this work, we use synchronous recognition strategy that takes advantage radical nucleophilic activation discriminate between secondary primary amines. Specifically, copper catalyst preferentially oxidizes species, whereas cobalt carbonylates produce amides. Coupling these fragments by cooperative catalysis produces with high selectivity, as showcased modification 41 biologically active compounds six drugs.

Язык: Английский

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Copper‐Catalyzed 1,2‐Trifluoromethylation Carbonylation of Unactivated Alkenes: Efficient Access to β‐Trifluoromethylated Aliphatic Carboxylic Acid Derivatives

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(49), С. 25787 - 25792

Опубликована: Окт. 9, 2021

A novel copper-catalyzed carbonylative trifluoromethylation of unactivated alkenes has been developed. broad range β-trifluoromethylated carboxylic acid derivatives were prepared in moderate to excellent yields from simple with regioselectivity. It is noteworthy that ethylene gas, as the simplest olefin, can also be applied directly obtain amides and ester. This transformation presents first example on alkenes.

Язык: Английский

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Iron‐Catalyzed Alkoxycarbonylation of Alkyl Bromides via a Two‐Electron Transfer Process

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(43)

Опубликована: Сен. 8, 2022

Transition metal-catalyzed carbonylative cross-coupling reactions are some of the most widely used methods in organic synthesis. However, despite obvious advantages iron as an abundant and low toxicity transition metal catalyst, its practical application carbonylation reaction remains largely unexplored. Here we report our recent study on Fe-catalyzed alkoxycarbonylation alkyl halides. Mechanistic studies indicate that is catalyzed by situ generated Fe2- complex. This low-valent species activates bromides via a distinctive two-electron transfer (TET) process, whereas it proceeds single electron (SET) process for iodides which consistent with literature.

Язык: Английский

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Copper‐Catalyzed 1,2‐Dicarbonylative Cyclization of Alkenes with Alkyl Bromides via Radical Cascade Process

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(49)

Опубликована: Окт. 18, 2022

Herein, we developed a new procedure on 1,2-dicarbonylative cyclization of 4-aryl-1-butenes with alkyl bromides. Using simple copper catalyst, two molecules carbon monoxide were introduced into the double bond formation four C-C bonds and ring. Various α-tetralones 2,3-dihydroquinolin-4-ones formed in moderate to good yields.

Язык: Английский

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