Radical Decarboxylative Carbometalation of Benzoic Acids: A Solution to Aromatic Decarboxylative Fluorination

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(14), P. 5349 - 5354

Published: April 5, 2021

Abundant aromatic carboxylic acids exist in great structural diversity from nature and synthesis. To date, the synthetically valuable decarboxylative functionalization of benzoic is realized mainly by transition-metal-catalyzed cross couplings. However, high activation barrier for thermal carbometalation that often requires 140 °C reaction temperature limits both substrate scope as well suitable reactions can sustain such conditions. Numerous reactions, example, fluorination developed aliphatic acids, are out reach counterparts with current chemistry. Here, we report a conceptually different approach through low-barrier photoinduced ligand to metal charge transfer (LMCT)-enabled radical strategy, which generates putative high-valent arylcopper(III) complex, versatile facile reductive eliminations occur. We demonstrate suitability our new address previously unrealized general acids.

Language: Английский

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Photoinduced Hydrocarboxylation via Thiol-Catalyzed Delivery of Formate Across Activated Alkenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13022 - 13028

Published: Aug. 12, 2021

Herein we disclose a new photochemical process to prepare carboxylic acids from formate salts and alkenes. This redox-neutral hydrocarboxylation proceeds in high yields across diverse functionalized alkene substrates with excellent regioselectivity. operationally simple procedure can be readily scaled batch at low photocatalyst loading (0.01% photocatalyst). Furthermore, this reaction leverage commercially available carbon isotologues enable the direct synthesis of isotopically labeled acids. Mechanistic studies support working model involving thiol-catalyzed radical chain wherein atoms are delivered substrate via CO2•– as key reactive intermediate.

Language: Английский

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Advances in the Methods for the Synthesis of Carbon Dots and Their Emerging Applications

Polymers, Journal Year: 2021, Volume and Issue: 13(18), P. 3190 - 3190

Published: Sept. 20, 2021

Cutting-edge technologies are making inroads into new areas and this remarkable progress has been successfully influenced by the tiny level engineering of carbon dots technology, their synthesis advancement impressive applications in field allied sciences. The advances science its conjugation with interdisciplinary fields emerged making, controlled characterization faster, cheaper as well more reliable products various scientific domains. Thus, a era nanotechnology developed technology. understanding generation process, control on processes selected such energy storage, environmental monitoring, catalysis, contaminates detections complex forensics, drug delivery, targeting other biomedical applications, etc., among most promising thus it is prominent area research today. In regard, types dot nanomaterials oxides, composites conjugations, have garnering significant attention due to potential energy, environment present paper highlights role importance dots, recent advancements methods, properties emerging applications.

Language: Английский

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A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8296 - 8305

Published: April 29, 2022

Aryl halides are a fundamental motif in synthetic chemistry, playing critical role metal-mediated cross-coupling reactions and serving as important scaffolds drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope existing halodecarboxylation methods remains limited, there currently exists no unified strategy that provides access to any type halide from an acid precursor. Herein, we report general catalytic method for direct halogenation (hetero)aryl via ligand-to-metal charge transfer. This accommodates exceptionally broad substrates. We leverage radical intermediate toward divergent pathways: (1) atom transfer bromo- or iodo(hetero)arenes (2) capture by copper subsequent reductive elimination generate chloro- fluoro(hetero)arenes. The proposed mechanism is supported through array spectroscopic studies.

Language: Английский

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Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20201 - 20206

Published: Oct. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Language: Английский

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Decarboxylative Borylation and Cross-Coupling of (Hetero)aryl Acids Enabled by Copper Charge Transfer Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(14), P. 6163 - 6172

Published: April 4, 2022

We report a copper-catalyzed strategy for arylboronic ester synthesis that exploits photoinduced ligand-to-metal charge transfer (LMCT) to convert (hetero)aryl acids into aryl radicals amenable ambient-temperature borylation. This near-UV process occurs under mild conditions, requires no prefunctionalization of the native acid, and operates broadly across diverse aryl, heteroaryl, pharmaceutical substrates. also one-pot procedure decarboxylative cross-coupling merges catalytic LMCT borylation palladium-catalyzed Suzuki-Miyaura arylation, vinylation, or alkylation with organobromides access range value-added products. The utility these protocols is highlighted through development heteroselective double-decarboxylative C(sp2)-C(sp2) coupling sequence, pairing halogenation processes two distinct (including substrates) subsequent cross-coupling.

Language: Английский

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Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(22), P. 12313 - 12370

Published: Nov. 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

Language: Английский

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Radical-Mediated Decarboxylative C–C and C–S Couplings of Carboxylic Acids via Iron Photocatalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 1110 - 1115

Published: Jan. 26, 2024

Despite the significant success of decarboxylative radical reactions, catalytic systems vary considerably upon different acceptors, requiring renewed case-by-case reaction optimization. Herein, we developed an iron condition that enables highly efficient decarboxylation various carboxylic acids for a range transformations. This operationally simple protocol was amenable to wide array delivering structurally diverse oxime ethers, alkenylation, alkynylation, thiolation, and amidation products in useful excellent yields (>40 examples, up 95% yield).

Language: Английский

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Utilization of C(sp³)‐Carboxylic Acids and Their Redox‐Active Esters in Decarboxylative Carbon−Carbon Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(15), P. 3693 - 3736

Published: May 11, 2021

Abstract Over the last several years, radical‐mediated decarboxylative cross‐coupling reactions employing alkyl carboxylic acids have emerged as a powerful tool for regiospecific construction of carbon−carbon bonds. Under thermal or photocatalytic conditions, wide variety C( sp 3 )‐carboxylic and their redox‐active esters undergo C−C bond formation with suitable reactant partners, leading to complex chemical scaffolds wide‐ranging applications. This synthetic strategy has advantages over more conventional organometallic reagents, including abundant starting material availability high functional group tolerance associated mild reaction conditions. review article highlights recent developments in functionalization α‐heteroatom‐substituted well challenging unactivated acids, representative examples discussed against backdrop insightful comments on mechanisms. In addition, synthesis natural products, drug molecules, late‐stage modification bioactive molecules this non‐traditional are included. been categorized into three main sections that organized around type being forged: )−C( 2 ), ). Further, separately each section. magnified image

Language: Английский

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