Electrifying Redox-Neutral Palladium-Catalyzed Carbonylations: Multielectron Transfer as a Catalyst Driving Force DOI
Pierre‐Louis Lagueux‐Tremblay, Kwok‐Cheong Tam,

Meijing Jiang

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

Palladium-catalyzed bond-forming reactions such as carbonylations offer an efficient and versatile avenue to access products from often feedstock reagents. However, the use of catalysts also comes with a cost, their need be regenerated after each product-forming cycle requires balancing thermal operations. The latter can lead high barriers even well restrict application many products. We introduce herein alternative approach palladium catalyst design, where instead electrochemical potential drive catalysis by continual two-electron cycling metal oxidation state. power behind these redox steps offers route carry out carbonylation reactions, including catalytic synthesis high-energy aroyl halide electrophiles, at unprecedentedly mild ambient temperature pressure. More generally, analysis suggests this functions distinct multi-electron exchange pathway, reduction enables oxidative addition drives product elimination. combination creates unique platform both reverse operations are favored in same system energy only added source.

Язык: Английский

Recent Advances in Visible Light Induced Palladium Catalysis DOI
Sumon Sarkar, Kelvin Pak Shing Cheung, Vladimir Gevorgyan

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(9)

Опубликована: Ноя. 14, 2023

Visible light-induced Pd catalysis has emerged as a promising subfield of photocatalysis. The hybrid nature radical species enabled wide array radical-based transformations otherwise challenging or unknown via conventional chemistry. In parallel to the ongoing pursuit alternative, readily available precursors, notable discoveries have demonstrated that photoexcitation can alter not only oxidative addition but also other elementary steps. This Minireview highlights recent progress in this area.

Язык: Английский

Процитировано

50
Pd(0)/Blue Light Promoted Carboiodination Reaction – Evidence for Reversible C–I Bond Formation via a Radical Pathway DOI
Austin D. Marchese, Andrew G. Durant, Cian M. Reid

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(45), С. 20554 - 20560

Опубликована: Окт. 28, 2022

A Pd(0)/blue light catalyzed carboiodination reaction is reported. simple, air-stable catalytic system, utilizing [Pd(allyl)Cl]2 and DPEPhos, generated a variety of iodinated hetero- carbocycles including oxindoles, dihydrobenzofurans, indolines, chromane, tetrahydronaphthalene. This protocol was tolerant sensitive functional groups free carboxylic acids, phenols, anilines, as well pyridines, while delivering products in up to 94% yield. Support for reversible C–I bond formation via single electron mechanism obtained using deuterium labeled substrate stoichiometric neopentylpalladium species.

Язык: Английский

Процитировано

51
Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments DOI Creative Commons
Hunter S. Sims, Mingji Dai

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

Процитировано

40
Visible Light Photoredox-Catalyzed Decarboxylative Alkylation of 3-Aryl-Oxetanes and Azetidines via Benzylic Tertiary Radicals and Implications of Benzylic Radical Stability DOI Creative Commons
Maryne A. J. Dubois, Juan J. Rojas, Alistair J. Sterling

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(10), С. 6476 - 6488

Опубликована: Март 3, 2023

Four-membered heterocycles offer exciting potential as small polar motifs in medicinal chemistry but require further methods for incorporation. Photoredox catalysis is a powerful method the mild generation of alkyl radicals C–C bond formation. The effect ring strain on radical reactivity not well understood, with no studies that address this question systematically. Examples reactions involve benzylic are rare, and their challenging to harness. This work develops functionalization oxetanes azetidines using visible light photoredox prepare 3-aryl-3-alkyl substituted derivatives assesses influence heterosubstitution small-ring radicals. 3-Aryl-3-carboxylic acid suitable precursors tertiary oxetane/azetidine which undergo conjugate addition into activated alkenes. We compare oxetane other systems. Computational indicate Giese additions unstrained acrylates reversible result low yields dimerization. Benzylic part strained ring, however, less stable more π-delocalized, decreasing dimer increasing product Oxetanes show high due Bent's rule rendering irreversible.

Язык: Английский

Процитировано

26
Light-Mediated Synthesis of Aliphatic Anhydrides by Cu-Catalyzed Carbonylation of Alkyl Halides DOI

Pinku Tung,

Neal P. Mankad

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

Процитировано

26
Escape from Hydrofunctionalization: Palladium Hydride‐Enabled Difunctionalization of Conjugated Dienes and Enynes DOI Creative Commons
Ziyan Zhang, Vladimir Gevorgyan

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(47)

Опубликована: Окт. 3, 2023

Abstract Palladium hydrides are traditionally employed in hydrofunctionalization (i.e. monofunctionalization) of conjugated dienes and enynes, owning to its facile protic hydropalladation electron‐rich (or neutral) unsaturated bonds. Herein, we report a mild PdH‐catalyzed difunctionalization enynes. This protocol is enabled by the chemoselectivity switch initial step achieved visible light enhancement hydricity PdH species. method allows for cascade annulation enynes with various easily available abundant substrates, such as acrylic acids, amides, Baylis–Hillman adducts, toward wide range alkenyl or alkynyl lactones, lactams, tetrahydrofurans. also provides an easy access complex spiro‐fused tricyclic frameworks.

Язык: Английский

Процитировано

18
Mononuclear palladium(I) and palladium(III) coordination compounds DOI

Siddhartha Banerjee,

Sagnik Chakrabarti,

Bailey S. Bouley

и другие.

Coordination Chemistry Reviews, Год журнала: 2025, Номер 535, С. 216605 - 216605

Опубликована: Март 17, 2025

Процитировано

1
Shining Visible Light on Reductive Elimination: Acridine–Pd-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids DOI
Naoyuki Toriumi,

Tomonori Inoue,

Nobuharu Iwasawa

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(42), С. 19592 - 19602

Опубликована: Окт. 11, 2022

Despite the recent tremendous progress on transition-metal/photoredox dual catalysis in organic synthesis, single transition-metal under visible-light irradiation, which can utilize light energy more efficiently, is still underdeveloped. Herein, we report design of photosensitizing phosphinoacridine bidentate ligands for visible-light-induced catalysis, expecting that electron-accepting acridine moiety would create a highly reactive electron-deficient metal center toward reductive elimination via metal-to-ligand charge transfer (MLCT). Using these ligands, have achieved palladium-catalyzed cross-coupling reaction aryl halides with carboxylic acids irradiation. Electronic tuning not only enabled use variety as coupling partner, including less chlorides, blue but also realized employment lower-energy green and red cross-coupling. Experimental mechanistic studies proved esters induced by photoirradiation phosphinoacridine-ligated arylpalladium(II) carboxylate complexes. The theoretical calculation suggests excited state promoted decreasing electron density Pd through photoinduced intramolecular transfer, i.e., MLCT, transition owing to scaffold. This very rare example palladium(II)

Язык: Английский

Процитировано

29
A Visible Light Driven Nickel Carbonylation Catalyst: The Synthesis of Acid Chlorides from Alkyl Halides DOI

Kristian El Chami,

Yi Liu,

Mohammed A. Belahouane

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(10)

Опубликована: Дек. 28, 2022

We describe here the development of a visible light driven nickel carbonylation catalyst. The combination large bite-angle Xantphos ligand with nickel(0) generates catalyst capable activating alkyl halides toward at ambient temperature in presence blue irradiation, and reductive elimination high energy acid chloride products. Unlike classical carbonylations, where coordination carbon monoxide inhibits reactivity earth abundant catalysts, CO-associated is found to be active reaction. Coupling build-up chlorides nucleophile addition can used access various amides, esters thioesters, including those sterically encumbered substrates or metal-reactive functionalities.

Язык: Английский

Процитировано

27
Palladium‐Catalyzed Direct Carbonylation of Bromoacetonitrile to Synthesize 2‐Cyano‐N‐acetamide and 2‐Cyanoacetate Compounds DOI Creative Commons
Zhipeng Bao, Xiao‐Feng Wu

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 14, 2023

Nitrile compounds containing ester and amide groups are important functionalized chemicals in synthetic medicinal chemistry. In this article, an efficient convenient palladium-catalyzed carbonylative procedure toward 2-cyano-N-acetamide 2-cyanoacetate has been developed. The reaction proceeds under mild conditions via radical intermediate which is suitable for late-stage functionalization. Gram-scale experiment was performed successfully low catalyst loading gave the target product excellent yield. Additionally, transformation can be atmospheric pressure provide alternative routes to 7 drug precursors.

Язык: Английский

Процитировано

14