Carbon Monoxide as C1 Building Block in Fine Chemical Synthesis^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(2), P. 199 - 221

Published: Sept. 20, 2023

Comprehensive Summary Carbon monoxide (CO) has become one of the most relevant and versatile renewable C1 building blocks for chemical synthesis, especially in fine chemicals industry, due to development efficient selective catalysts its activation. In this review, we present a comprehensive critical analysis last 10 years literature on use CO as feedstock production. The review is organized by type catalytic reaction, namely alkene alkyne carbonylation, hydroformylation, carbonylation aryl halides, carbonylative cross‐coupling C—H carbonylation. Notable examples synthesis and/or known pharmaceuticals are highlighted. Emphasis placed utilizing block or more steps. catalyst used reaction conditions consistently presented throughout all examples.

Language: Английский

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Palladium‐Catalyzed Direct Carbonylation of Bromoacetonitrile to Synthesize 2‐Cyano‐N‐acetamide and 2‐Cyanoacetate Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 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.

Language: Английский

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Versatile stereoselective oxidative alkoxycarbonylation of styrenes at room-temperature

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 432, P. 115397 - 115397

Published: March 1, 2024

Carbonylation reactions carried out at room temperature and atmospheric pressure of carbon monoxide are highly attractive extremely rare the same time. Here, oxidative alkoxycarbonylation styrenes to industrially relevant cinnamates has been developed under such a mild conditions (rt, 1 atm CO) in presence palladium(II) complex bearing bis(aryl)acenaphthenequinonediimine ligand, benzoquinone p-toluenesulfonic acid. Remarkably, variously substituted styrene derivatives have efficiently carbonylated using nearly stoichiometric amount alcohols, with dramatic reduction waste. Even reluctant internal alkenes shown be compatible these carbonylative conditions. In consideration experimental results DFT calculations mechanistic rationale proposed. Based on this study, found promote final palladium reoxidation, boost reaction unprecedent The present methodology successfully exploited for synthesis high value-added cinnamoyl glycerols cinnamic acid sugar esters, including 6-O-p-coumaroyl-D-glucose natural product.

Language: Английский

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Light-Driven Three-Component Carbonylation of Aryl Halides Using Abundant Metal Carbonyl

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2169 - 2174

Published: March 13, 2024

Carbonyl compounds are widely found in various pharmaceutical intermediates and synthetic precursors. Herein we report a simple light-driven three-component aryl halide process for synthesizing variety of carbonylation products, utilizing Co2(CO)8 as an abundant solid carbonyl source, good to excellent yields. The products can easily be subjected further functionalization synthesis. Mechanism studies indicated that this reaction is enabled by radical generation the subsequent CO insertion, alkene protonation process.

Language: Английский

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Umpolung‐Enabled Divergent Dearomative Carbonylations

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three-dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π-bonds through umpolung chromium-arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO-gas-free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3- 1,4-cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late-stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

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An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO₂ as a CO Surrogate

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 22, 2024

Abstract The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long‐standing challenge to synthetic chemists. Herein, we propose catalyst cascade Scheme in which 2 is used as surrogate the benzyl chlorides. Our approach based on cooperation between two coexisting catalytic cycles: ‐to‐CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso‐tetraphenylporphyrin) and an electrochemical catalyzed [Ni(bpy)Br ] (2,2′‐bipyridine). As proof concept, this protocol allows for synthesis symmetric ketones from good excellent yields undivided cell with non‐sacrificial electrodes. reaction can be directly scaled up gram‐scale operates effectively at concentration 10 %, demonstrating its robustness. mechanistic studies cyclic voltammetry, IR spectroelectrochemistry Density Functional Theory calculations suggest synergistic effect catalysts. produced reduction key formation [Ni(bpy)(CO) ], proposed intermediate responsible C−C bond steps.

Language: Английский

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Effect of I- ligand and surface oxygen-containing groups on catalytic activity and stability of activated carbon-supported Pd catalysts in acetylene dicarbonylation

Fuel, Journal Year: 2024, Volume and Issue: 366, P. 131389 - 131389

Published: March 5, 2024

Language: Английский

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Pd-Catalyzed Aerobic C–H Carbonylative Esterification of Imidazo[1,2-a]pyridines with Alcohols as the Carbonyl Source

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

A simple and practical method has been developed for the carbonylative esterification of imidazo[1,2-a]pyridines via C(sp2)-H bond functionalization using alkyl alcohols under mild reaction conditions. The carbonyl fragment is sourced from radical-mediated C-C cleavage alcohols, providing a green, safe, economic alternative to traditional sources like carbon monoxide. Through this strategy, number imidazo[1,2-a]pyridine-3-carboxylates were obtained substrates by single step.

Language: Английский

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Observation of Aromatic B₁₃(CO)_n⁺ (n = 1–7) as Boron Carbonyl Analogs of Benzene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31464 - 31471

Published: Nov. 7, 2024

CO as a typical σ-donor is one of the most important ligands in chemistry, while planar B

Language: Английский

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Palladium-catalyzed alkyne hydrocarbonylation under atmospheric pressure of carbon monoxide in the presence of hydrosilane

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(3), P. 1120 - 1127

Published: Jan. 1, 2023

An ultramild reaction condition for the hydrocarbonylation of alkynes, which is performed under atmospheric pressure CO in absence acids, has been developed.

Language: Английский

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