Electron-Catalyzed Aminocarbonylation: Synthesis of α,β-Unsaturated Amides from Alkenyl Iodides, CO, and Amines

Picard, Baptiste; Fukuyama, Takahide; Bando, Takanobu; Hyodo, Mamoru; Ryu, Ilhyong

doi:10.1021/acs.orglett.1c03714

Cited by 6 publications

(6 citation statements)

References 41 publications

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“…Encouraged by the formation of variable amounts of single carbonylation product amide 4aa in the double carbonylation processes, we proceeded to identify suitable conditions to improve the selectivity of single carbonylation for the synthesis of amide 4aa . In the context of photochemical synthesis, many redox or simple electron-transfer steps that are estimated to be endergonic by simple comparison of redox potentials become exergonic when additives were added. , Also, drawing inspiration from the N -philic mode of acyl radicals pioneered by Ryu, − we attempted to add various amines such as bases, Lewis bases, or π-systems to tune the single carbonylation selectivity. We were pleased to discover that the addition of stoichiometric 4-dimethylaminopyridine (DMAP) (3.0 equiv) could completely reverse the product distribution to the predominant formation of single carbonylation product 4aa under otherwise identical conditions (98% yield, Figure C).…”

Section: Resultsmentioning

confidence: 99%

“…The lowest unoccupied molecular orbital allowed such a radical class to act as electrophiles to react with nucleophiles, such as amines and electron-rich π-systems. For example, a range of pioneering studies by Ryu demonstrated that acyl radicals could also react as electrophilic radicals toward amines, selectively leading to various highly functionalized mono carbonylation amide products. − Moreover, combined experimental and density functional theory (DFT) computational studies by the groups of Ryu and Schiesser have also disclosed that acyl radicals were able to mask as electrophiles to attack at the most nucleophilic end of NC π-systems, providing a powerful method for the synthesis of various nitrogen-containing compounds . Drawing inspiration from these works, we think the philicity-regulation strategy would probably allow the development of switchable radical carbonylation reactions.…”

Section: Introductionmentioning

confidence: 99%

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Switchable Radical Carbonylation by Philicity Regulation

Lü

et al. 2022

J. Am. Chem. Soc.

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Carbonylation reactions involving CO as readily available C1 synthons have become one of the most important tools for the construction of carbonyl compounds from feedstock chemicals. Despite numerous catalytic methods for carbonylation reactions proceeding via ionic or radical pathways, an inherent limitation to these methods is the need to control switchable single and double carbonylative formation of value-added products from the same and simple starting materials. Here, we describe a new strategy that exploits photoredox catalysis to regulate the philicity of amine coupling partners to drive switchable radical carbonylation reactions. In double carbonylation, amines were first transformed into nitrogen radical cations by single-electron transfer-oxidation and coupled with CO to form carbamoyl radicals, which further underwent radical cross-coupling with the incipient cyanoalkyl acyl radicals to afford the double carbonylation products. Upon the addition of stoichiometric 4dimethylaminopyridine (DMAP), DMAP competitively traps the initially formed cyanoalkyl acyl radical to form the relatively stabilized cyanoalkyl acyl-DMAP salts that engaged in the subsequent substitution with the nucleophilic amines to produce the single carbonylation products. The reaction proceeded smoothly with excellent selectivity in the presence of various amine nucleophiles at room temperature, generating valuable amides and α-ketoamides in a versatile and controlled fashion. Combined experimental and computational studies provided mechanistic insights into the possible pathways.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Switchable Radical Carbonylation by Philicity Regulation

Lü

et al. 2022

J. Am. Chem. Soc.

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“…The electron-catalyzed aminocarbonylation strategy was extended to alkenyl iodides (Scheme 9). 39 This process was found to be compatible with various amines and alkenyl iodides, and the bioactive Ilepcimide could be synthesized using this protocol. Alkenyl bromides, however, were not converted under these conditions.…”

Section: Alkenyl Radical Carbonylation Accompanied By Electron Transfermentioning

confidence: 95%

New directions in radical carbonylation chemistry: combination with electron catalysis, photocatalysis and ring-opening

et al. 2022

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“…Like quinazoline α, β-Unsaturated amides [80] and maleimides [81] are fundamental building blocks of many biologically active compounds. Peng et al again, in the following year, synthesized α,β-unsaturated amides, and maleimides by palladium-catalyzed carbonylative divergent synthesis (Scheme 21).…”

Section: Metal Carbonyl As Co Sourcementioning

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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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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Electron-Catalyzed Aminocarbonylation: Synthesis of α,β-Unsaturated Amides from Alkenyl Iodides, CO, and Amines

Cited by 6 publications

References 41 publications

Switchable Radical Carbonylation by Philicity Regulation

Switchable Radical Carbonylation by Philicity Regulation

New directions in radical carbonylation chemistry: combination with electron catalysis, photocatalysis and ring-opening

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

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