Palladium-catalysed amino-vs. Alkoxycarbonylation of iodoalkenes using bifunctional N,O-nucleophiles

Mikle, Gábor; Noveczky, Péter; Mahó, Sándor; Kollár, László

doi:10.1016/j.tet.2021.132050

Cited by 5 publications

(5 citation statements)

References 31 publications

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“…This complex can react with nucleophiles like alcohols, primary amines, and secondary amines to give carboxylic acid derivatives, i. e., esters and amides. [23,24] Mikle et al found this step to be rate-determining. When primary and secondary amines act as nucleophiles, no extra-base like KOAc, TlOAc, or K 2 CO 3 is required because they can act as a base and neutralize the acid formed in the reaction.…”

Section: Via Carbonylation Of Iodoalkenes and Enol Triflatesmentioning

confidence: 99%

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A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates

Pant,

Prakash,

Dhami

2024

ChemistrySelect

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Catalytic carbonylation has gained a lot of interest over the past 20 years. It produced various pharmaceuticals, agrochemicals, and intermediates that can made through this process. The carbonylation process is the most straightforward method to insert CO into any organic substrate using a simple carbonyl source, i. e., CO gas. Apart from gaseous CO, many techniques have devised for producing CO in situ using surrogates such as HCOOH, DMF, Formic acid, Phenyl Formate, Oxalic acid, and Chloroform. Several carbonylation methods, such as aminocarbonylation, alkoxycarbonylation, double carbonylation, and oxidative carbonylation, provide viable and appealing substitutes for conventional synthetic methods on a commercial or laboratory scale. Many recent studies focus on catalyst‐product separation, catalyst recoverability, and reusability in these reactions. Therefore, advancements in using different approaches, such as supported liquid phase catalysis and biphasic catalysis, to anchor homogeneous catalysts are becoming increasingly important. These carbonylation methods are easy to use, cost‐effective, and do not require ligands. They also produce excellent yields of the products necessary. Using phosphine ligands has drawbacks, including high work‐up costs, laborious work‐up techniques, and sensitivity to air and moisture. Several phosphine‐free carbonylation pathways offer affordable and straightforward ways to accomplish these changes without phosphine ligands. This review summarizes the synthetic application of homogeneous and immobilized catalysts in producing carboxylic acid derivatives and heterocycles that have medicinal properties.

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Section: Via Carbonylation Of Iodoalkenes and Enol Triflatesmentioning

confidence: 99%

“…In the next carbonylation step, the intermediate forms α‐β‐unsaturated acyl palladium complex. This complex can react with nucleophiles like alcohols, primary amines, and secondary amines to give carboxylic acid derivatives, i. e., esters and amides [23,24] . Mikle et al.…”

Section: Catalytic Carbonylation Via Homogeneous Catalytic Routementioning

confidence: 99%

A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates

Pant,

Prakash,

Dhami

2024

ChemistrySelect

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“…Scheme 56 Synthesis of biologically relevant phthalides by intramolecular alkoxycarbonylation Kollár [114] described an efficient carbonylation strategy, using N,O-nucleophiles, for the synthesis of unprecedented bifunctional amide-ester compounds. The aminocarbonylation of 2-iodobornene and steroids with iodoalkene functionality was followed by alkoxycarbonylation, both catalyzed by Pd(OAc) 2 /PPh 3 , in the presence of 1 bar CO, resulting in several amide-ester products, including biologically relevant steroid dimers (Scheme 57).…”

Section: Scheme 55 Synthesis Of Drugs By Co-catalyzed Phenoxycarbonyl...mentioning

confidence: 99%

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

Carrilho,

Calvete,

Mikle

et al. 2023

Chin. J. Chem.

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Carbon 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.This article is protected by copyright. All rights reserved.

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“…Good isolated yields of dicarboxamides were obtained with aromatic and aliphatic diamines, as well. Recently, we investigated the carbonylation of iodoalkenes in the presence of heterobifunctional ethanolamines as O,N-nucleophiles . Carboxamides were isolated as major products, but the corresponding amide ester derivatives were also detected in the reaction mixture.…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles

et al. 2023

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Palladium-catalyzed amino-and alkoxycarbonylation reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity. In addition to the model ethanolamine/iodobenzene system, various heteroaromatic substrates and numerous related nucleophiles were tested under optimized conditions, providing moderate to good yields of the target compounds. Reactions of serinol and 1,3-diamino-2-propanol as model trifunctional compounds showed particularly high chemoselectivity on amide ester products. Considering the coordinative properties of the applied nucleophiles, a rational catalytic cycle was proposed.

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Palladium-catalysed amino-vs. Alkoxycarbonylation of iodoalkenes using bifunctional N,O-nucleophiles

Cited by 5 publications

References 31 publications

A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates

A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates

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

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles

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Palladium-catalysed amino-vs. Alkoxycarbonylation of iodoalkenes using bifunctional N,O-nucleophiles

Cited by 5 publications

References 31 publications

A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates

A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates

Carbon Monoxide as C1 Building Block in Fine Chemical Synthesis†

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles

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