Double Carbonylation Of Aryl Iodides Research Articles

Ligand-free Zn-catalyzed double carbonylation of aryl iodides with secondary amines: A simple and efficient approach to access α-ketoamides

Herein, we report a Zinc catalyzed double carbonylation of aryl iodides with secondary amines under CO pressure for the synthesis of α-ketoamides in good to excellent yields. This methodology provides a simple and economic approach to derivatize useful α-ketoamides.

Mono- and double carbonylation of aryl iodides with amine nucleophiles in the presence of recyclable palladium catalysts immobilised on a supported dicationic ionic liquid phase

Silica modified with organic dicationic moieties proved to be an excellent support for palladium catalysts used in the aminocarbonylation of aryl iodides.

Double Carbonylation of Aryl Iodides Promoted by CTF-Supported Palladium

Double Carbonylation of Aryl Iodides Promoted by CTF-Supported Palladium

Covalent triazine framework-supported palladium as a ligand-free catalyst for the selective double carbonylation of aryl iodides under ambient pressure of CO.

Carbonylation of aryl iodides with amines under atmospheric pressure of CO, catalyzed by Pd/CTFs (covalent triazine frameworks) without any specific additives, leads to the highly selective synthesis of α-ketoamides.

ChemInform Abstract: Ligand‐Free Pd‐Catalyzed Double Carbonylation of Aryl Iodides with Amines to α‐Ketoamides under Atmospheric Pressure of Carbon Monoxide and at Room Temperature.

AbstractIn situ generation of Pd nanoparticles in PEG‐400 is the key to the first general, ligand‐ and additive‐free protocol for double carbonylation of aryl iodides in the presence of amines to furnish α‐ketoamides.

Ligand-Free Pd-Catalyzed Double Carbonylation of Aryl Iodides with Amines to α-Ketoamides under Atmospheric Pressure of Carbon Monoxide and at Room Temperature.

A general Pd-catalyzed double carbonylation of aryl iodides with secondary or primary amines to produce α-ketoamides at atmospheric CO pressure has been developed. This transformation proceeds successfully even at room temperature and in the absence of any ligand and additive. A wide range of aryl iodides and amines can be coupled to the desired α-ketoamides in high yields with excellent chemoselectivities. Importantly, the current methodology has been demonstrated to be applied in the synthesis of bioactive molecules and chiral α-ketoamides.

ChemInform Abstract: Phosphine‐Free, Efficient Double Carbonylation of Aryl Iodides with Amines Catalyzed by Water‐Insoluble and Water‐Soluble N‐Heterocyclic Carbene—Amine Palladium Complexes.

AbstractThe water‐soluble catalyst can be recovered by simple extraction and reused for up to three times without significant decrease of the product yields.

Double carbonylation of aryl iodides with amines under an atmospheric pressure of carbon monoxide using sulfur-modified Au-supported palladium

A double carbonylation of aryl iodides with amines proceeded by using Pd nano particles leached from SAPd to give α-ketoamides.

Phosphine‐Free, Efficient Double Carbonylation of Aryl Iodides with Amines Catalyzed by Water‐Insoluble and Water‐Soluble N‐Heterocyclic Carbene–Amine Palladium Complexes

AbstractThe water‐insoluble and water‐soluble N‐heterocyclic carbene (NHC)–amine palladium complexes, Ipr‐Pd(deba)Cl and SO3‐Ipr‐Pd(deba)Cl, were synthesized. Both catalysts exhibit excellent activity in the phosphine‐free double carbonylation of aryl iodides with amines to produce α‐keto amides. Moreover, as the water‐soluble catalyst exhibits significant compatibility in the aqueous phase with the activities of different Pd‐NHC complexes, we conclude that the intramolecular amine ligand strongly affects the selectivity of the products in double carbonylation reaction and serves as an alternative of phosphine ligands.magnified image

NHC‐Pd complex‐catalyzed double carbonylation of aryl iodides with secondary amines to α‐keto amides

A series of palladium–NHC compounds were prepared and their catalytic activity in the double carbonylation of aryl iodides to synthesize α‐keto amides were examined. Palladium complexes bearing mixed NHC–phosphine exhibited high efficiency for the double carbonylation reaction. The effects of different solvents, base, temperature, carbon monoxide (CO), pressure, various amine and aryl iodides were investigated. Both electron‐rich and electron‐deficient aryl iodides afforded the corresponding substituted α‐keto amides in moderate to good yields. A possible mechanism was also proposed. Copyright © 2013 John Wiley & Sons, Ltd.

Palladium-Catalyzed Double Carbonylation Using Near Stoichiometric Carbon Monoxide: Expedient Access to Substituted 13C2-Labeled Phenethylamines

A novel and general approach for (13)C(2)- and (2)H-labeled phenethylamine derivatives has been developed, based on a highly convergent single-step assembly of the carbon skeleton. The efficient incorporation of two carbon-13 isotopes into phenethylamines was accomplished using a palladium-catalyzed double carbonylation of aryl iodides with near stoichiometric carbon monoxide.

Palladium complexes grafted onto mesoporous silica catalysed the double carbonylation of aryl iodides with amines to give α-ketoamides

A promising route for the double carbonylation of aryl iodide derivatives with secondary and primary amines to produce α-ketoamides is described using covalently immobilized palladium complexes on SBA-15 silica. Adequate adjustments of the different reaction parameters (temperature, CO pressure, nature of base, solvent, substrate…) to achieve optimal catalyst performance were made using PdCl2(PPh2)2@SBA-15 as catalytic system. High conversions (up to 80%) and excellent selectivities (up to 96%) for the double carbonylated α-ketoamide products were obtained using K2CO3 as base, MEK or DMF as solvent and a 1 mol% [Pd] catalyst. We also demonstrated that two other palladium hybrid mesoporous materials can be alternatively used, namely PdCl2(PCy2)2@SBA-15 and PdCl2(PNP)@SBA-15, without loss of activity and selectivity. Finally, catalyst recycling of PdCl2(PPh2)2@SBA-15 showed that the catalyst could be reused for up to 3 cycles without affecting catalyst performance.

A phosphine-free Pd catalyst for the selective double carbonylation of aryl iodides

The first phosphine-free Pd-catalysed double carbonylation of aryl iodides is reported as a general and practical method, giving excellent conversions and selectivities for a wide range of aryl iodides and amine nucleophiles under atmospheric CO pressure.

A General and Efficient Copper Catalyst for the Double Carbonylation Reaction

The use of (NHC)CuI complex in combination with a N-heterocyclic carbene precursor as catalyst for the double carbonylation of aryl Iodides and secondary amines solves the problem of using the precious metal Pd and phosphine ligands. The new protocol requires a nonprecious metal catalyst and has greater generality than those previously reported.

Remarkable Ligand Effect on the Palladium‐Catalyzed Double Carbonylation of Aryl Iodides.

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Remarkable ligand effect on the palladium-catalyzed double carbonylation of aryl iodides

The use of t-Bu3P as a ligand dramatically improved the generality of the double carbonylation of aryl iodides, and Mo(CO)6 was also found to be effective as a CO source in the system.

Double Carbonylation of Aryl Iodides with Diethylamine Catalyzed by Dinuclear Palladium Complexes.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Double carbonylation of aryl iodides with diethylamine catalyzed by dinuclear palladium complexes

Dinuclear palladium complexes bridged by a novel PNNP ligand, N,N′-bis[(2-diphenylphosphino)phenylformamidinate (dpfam), were found to be very efficient and selective catalysts for the double carbonylation of iodobenzene with diethylamine using K 3PO 4 as base and 1,4-dioxane as solvent with a TON up to 10 5 and selectivity of 96%.

Double carbonylation of aryl iodides with primary amines under atmospheric pressure conditions using the Pd/PPh(3)/DABCO/THF system.

Double carbonylation of aryl iodides with primary amines under atmospheric pressure conditions using the Pd/PPh(3)/DABCO/THF system.

Mechanistic studies on palladium-catalyzed double carbonylation of aryl iodides affording α-keto esters

In relation to the mechanism of palladium-catalyzed carbonylation of aryl iodides to give α-keto esters, the carbonylation reactivity of some palladium complexes such as RPdIL 2 ( I: R = C 6H 5, L = P(C 6H 5) 3; II: R = C 6H 5CO, L = P(C 6H 5) 3) and C 6H 5COPd[P(C 6H 5) 3] 2(ClO 4)·acetone ( III) was investigated. In the carbonylation reaction in the presence of alcohols and t-amines, both complexes I and II exhibited the same reactivities. Complex II gave higher selectivities for α-keto esters when solvents of lower dielectric constant and lower donor number were used. The perchlorate complex III, which underwent double carbonylation with a high selectivity when treated with diethylamine and carbon monoxide, mainly gave simple esters in reactions with alcohols under carbon monoxide. The use of an alcohol in conjunction with a t-amine in the reaction of complex II could afford an α-keto ester, while the use of alkoxide resulted in exclusive formation of a simple ester. Heating of complex II with iodobenzene under carbon monoxide gave benzoyl iodide. These results are discussed in relation to the mechanism of catalytic double carbonylation.