Carbonylation Of Aryl Halides Research Articles

Carbon Monoxide as C1 Building Block in Fine Chemical Synthesis†

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

Carboxylation and Carbonylation of Aryl Halides by Formic Acid on a Li-Modified Pd/Co3O4 Catalyst

Key words palladium catalysis - catalyst support - carboxylation - carbonylation - aryl halides - formic acid

Carbonylation of Aryl Halides in the Presence of Heterogeneous Catalysts

Palladium-catalyzed carbonylation in the presence of organic and organometallic nucleophiles serves as a powerful tool for the conversion of aryl/alkenyl halides or halide equivalents to carbonyl compounds and carboxylic acid derivatives. To circumvent the difficulties in product separation and recovery and reuse of the catalysts, associated with homogeneous reactions, supported counterparts of the homogeneous palladium catalysts were developed. The review intends to summarize the huge development that has been witnessed in recent years in the field of heterogeneous carbonylation. A great plethora of supports, organic modifiers on solid surfaces stabilizing metal particles, transition metal precursors, as well as alternative sources for CO was investigated. In most cases, careful optimization of reaction conditions was carried out. Besides simple model reactions, the synthesis of carbonyl compounds and carboxylic acid derivatives from substrates with different functionalities was performed. In some cases, causes of palladium leaching were clarified with detailed investigations. The advantages of immobilized catalysts were shown by several examples. The possibility of catalystrecycling was proved besides proving that metal contamination of the products could often be kept below the detection limit. At the same time, detailed investigations should be carried out to gain a better insight into the real nature of these processes.

Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor

A transition-metal-free, carbon monoxide-free, and general methodology for carbonylative Suzuki coupling has been developed.

ChemInform Abstract: Construction of Benzimidazoles and Benzoxazoles Through the Molybdenum‐Mediated Carbonylation of Aryl Halides.

AbstractVarious substrates are tolerant to this facile and efficient one‐pot construction of the title compounds without the need of gaseous CO or Pd‐catalysis.

A review on transition-metal catalyzed C-H bond carbonylation reactions with CO

Carbon monoxide can be used as an inexpensive and readily available C1 source, which is also in agreement with atom economy. Carbonylation reactions with CO have been and continue to be a very active area of research. Since the pioneering work of Heck in 1974, carbonylations of aryl halides and pseudohalides with CO have become one of the most common methods for the addition of a carbonyl group to organic molecules. Recently, transition-metal-catalyzed chelation-assisted carbonylation of C-H bonds for the synthesis of carbonyl compounds. The progress in carbonylation chemistry has been achieved in both academic laboratories and industry. Hence, in this paper, we have reviewed the research work of transition-metal-catalyzed C-H bond carbonylation reactions with CO in recent years. We made introductions of C-H bond carbonylation reactions from three main parts: sp C-H, sp2 C-H and sp3 C-H bond. Some reaction mechanisms were described in the paper. These C-H bonds carbonylation reactions provide a simple and effective method for the synthesis of acids, ketones, esters, amides and anhydrides.

Construction of Benzimidazoles and Benzoxazoles through the Molybdenum‐Mediated Carbonylation of Aryl Halides

AbstractThe facile and efficient one‐pot construction of benzimidazoles and benzoxazoles through the Mo(CO)6‐mediated carbonylation of aryl halides was examined. In the process, Mo(CO)6 acted as a convenient and safe solid source of carbon monoxide. A wide range of substrates were tolerated to provide the corresponding products in fair to good yields without the need of gaseous CO or palladium catalysts.

ChemInform Abstract: Palladium‐Catalyzed Carbonylations of Aryl Bromides Using Paraformaldehyde: Synthesis of Aldehydes and Esters.

AbstractThe first successful application of readily available paraformaldehyde in a CO‐gas‐free synthetic protocol for palladium‐catalyzed carbonylations of aryl halides is reported.

Polymer supported Pd catalyzed thioester synthesis via carbonylation of aryl halides under phosphine free conditions

A new polymer anchored Pd(ii) complex has been synthesized and characterized. The catalytic performance of this complex has been tested for thioester synthesis via carbonylation of aryl halides and thiols under phosphine free conditions. This catalyst showed excellent catalytic activity and recyclability.

Palladium‐Mediated [11C]Carbonylation at Atmospheric Pressure: A General Method Using Xantphos as Supporting Ligand

AbstractThe palladium‐catalyzed [11C]carbonylation of aryl halides and triflates was achieved at atmospheric pressure by employing xantphos as the supporting ligand. Aryl halides were converted into their corresponding [11C]amides in good to excellent yields. The conditions were also successfully employed in the radiolabeling of an [11C]ester, a [11C]carboxylic acid, an [11C]aldehyde, and a [11C]ketone.

ChemInform Abstract: Molybdenum‐Mediated Carbonylation of Aryl Halides with Nucleophiles Using Microwave Irradiation.

AbstractThe process can be applied to the formation of various amides, sulfonamides and carboxylic acids/esters.

ChemInform Abstract: Effect of Substituent Character on Carbonylation of Aryl Halides in Two-Phase Systems.

ChemInform Abstract: Effect of Substituent Character on Carbonylation of Aryl Halides in Two-Phase Systems.

Carbonylation of Aryl Halides: Extending the Scope of the Reaction

Carbonylation reactions are being increasingly favoured in pharmaceutical chemistry for the atom-efficient introduction of carbonyl centres in aldehydes, acids, esters, and amides. Convenient procedures for simple aryl iodides and bromides are well established, and now the need is to develop improved conditions to allow the reactions to be extended to the more unreactive substrates, such as sterically hindered compounds and aryl chlorides. Sterically hindered compounds such as 2-iodo- or 2-bromo-m-xylenes can be converted using alkoxy and aminocarbonylation, while dehalogenation becomes a significant side reaction for reductive carbonylation. Less hindered compounds such as 2-iodo- or bromotoluene can be reacted successfully. Changing the aryl ligands of PdCl2{Ph2P(CH2)3PPh2} to alkyl groups improves the rate of oxidative addition but slows the carbonyl insertion step such that rates for the majority of aryl bromides are not improved by this change. Complexes such as PdCl2{Cy2P(CH2)3PCy2} offer better performance for alkoxy and aminocarbonylation of aryl chlorides. However, for reductive carbonylation dehalogenation is a significant side reaction. Increasing CO pressure results in additional CO coordination to the catalytic intermediates and slows the reaction, while the dehalogenation is little affected, so reaction selectivity suffers. Thus, CO pressure is a critical parameter, particularly for reductive carbonylation, in achieving the optimum performance.

Mechanism of the catalytic carbonylation of aryl halides with a modified cobalt carbonyl

Investigation of the mechanism of the carbonylation of aryl halides in a catalytic system consisting of cobalt carbonyl, terminal olefin oxide, and base showed that this catalytic system activates aryl halides via a radical anion mechanism. The kinetic regularities of the process together with IR spectral data suggest reversible formation of the active catalytic complex under the reaction condition. The complex is a cyclic metal lactone, and it can form not only from olefin oxide but also from its methanolysis product, the corresponding glycol monomethyl ether.

Synthesis of heteroaromatic carboxylic acids by carbonylation of hetaryl halides with catalysts based on cobalt carbonyl modified with epoxides

A new method for the synthesis of heteroaromatic acids and their derivatives (esters and salts) by carbonylation of the corresponding halides was developed. Hetaryl halides were activated in alcoholic-alkali medium by highly active catalytic systems based on cobalt carbonyl modified with epoxides, developed previously for carbonylation of aryl halides.

Efficient heterogeneously catalyzed amidocarbonylation of bromoarenes based on a serinol-derived chelate diphosphine ligand

Although carbonylation of aryl halides is widely applied in synthesis, heterogeneous catalysts for this transformation are scarce. In order to heterogeneously catalyze the amidocarbonylation of bromoarenes, a polymer-supported catalytic system was assembled from Pd(dba) 2 and a polymer-bound diphosphine chelate, prepared via solid-phase synthesis from serinol. The system efficiently converts aryl bromides into carboxamides in a reaction with CO and aliphatic or aromatic amines. Comparison with other supported phosphine ligands demonstrated the superiority of the chelate diphosphine structure. Remarkably, partial complexation of the polymer-tethered ligating sites with Pd forms notably better catalytic systems than the full complexation. The reactivity pattern of the catalytic system points to the oxidative addition as the rate-determining step of the catalytic cycle.

Synthesis of Aromatic Carboxylic Acids by Carbonylation of Aryl Halides in the Presence of Epoxide-Modified Cobalt Carbonyls as Catalysts

A new procedure was developed for synthesis of aromatic and heteroaromatic acids and their derivatives (esters, salts) by carbonylation of the corresponding aryl halides. The acids are selectively formed in a high yield under very mild conditions. Highly active catalytic systems, base-containing alcoholic solutions of cobalt carbonyl modified with epoxides, were used to activate aryl halides.

Synthesis of silica-supported poly-γ-diphenylarsinopropylsiloxane palladium complex and its catalytic behavior for Heck carbonylation of aryl halides

A silica-supported poly-γ-diphenylarsinopropylsiloxane palladium complex has been prepared from γ-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide in THF and then the reaction with palladium chloride. It is an efficient catalyst for Heck carbonylation of aryl halides under atmospheric pressure of carbon monoxide. This polymeric palladium catalyst can be recovered and reused.

ChemInform Abstract: Carbonylation of Aryl Halides and Vinyl Bromides Mediated by Tetracarbonylcobalt Anion.

AbstractReaction of the aryl halides (I) with octacarbonyl dicobalt (V) in the presence of MeI (II) and NaOH under phase‐transfer conditions gives mixtures of the ketones (III) + (IV).

ChemInform Abstract: Nickel Catalyzed Amidation of Bromo‐ and Iodobenzene.

Abstract The carbonylation of aryl halides in the presence of p -RC 6 H 4 NH 2 (R = H, CH 3 , Cl) or C 6 H 5 NHR (R = CH 3 , C 6 H 5 ) and a catalytic amount of a nickel(II) or nickel(0) tertiary phosphine complex at 150°C or above under carbon monoxide pressures is reported. Amides were obtained in high yields in reactions with p -RC 6 H 4 NH 2 , but with C 6 H 5 NHR compounds the expected N -alkyl benzanilides were not formed, benzanilide in low yield being formed instead. A possible catalytic cycle based on an active Ni o -carbonyl complex is suggested, and the observed deactivation of the catalytic system when the carbon monoxide pressure falls to 6 atm or below, is accounted for in terms of a side reaction which produces an inactive Ni II compound.