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

Kawamoto, Takuji; Fukuyama, Takahide; Picard, Baptiste; Ryu, Ilhyong

doi:10.1039/d2cc02700c

Cited by 9 publications

(2 citation statements)

References 79 publications

(69 reference statements)

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“…Then the alkyl radical D undergoes carbonylation with E to give the acyl manganese RCOMn (CO) 4 I intermediate F . 14 Intermediate F then reacts with an arylamine to form the final alkyl amide product and release the catalyst for the next catalytic cycle after the reductive elimination step.…”

Section: Resultsmentioning

confidence: 99%

Visible light-induced manganese-catalyzed aminocarbonylation of alkyl iodides under atmospheric pressure at room temperature

Zhao,

Gu,

2024

Org. Chem. Front.

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Section: Resultsmentioning

confidence: 99%

Visible light-induced manganese-catalyzed aminocarbonylation of alkyl iodides under atmospheric pressure at room temperature

Zhao,

Gu,

2024

Org. Chem. Front.

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“…In addition to the total avoidance of transition metals, those types of processes also display great promise due to their cleaner and increased atom-economic approach. However, because of their novelty, those methods are still actively developed, and strongly depend on the substrate ability to dissociate the R–X bond to achieve successful carbonylation. On the other hand, metal carbonylation has been an important topic of research since the pioneering work by Heck, almost 50 years ago .…”

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confidence: 99%

Phosphine-Free Aminocarbonylation Using Pd/DBU Catalyst: Carbonylative Coupling of Aryl Iodides and Amines

Picard

Fukuyama²,

Ryu

2022

J. Org. Chem.

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An improved carbonylation method allowing amide bond formation between aryl iodides and aromatic amines is presented. In contrast to usual methods based on Pd catalysis, this method does not require a phosphine ligand. The catalyst system simply employs bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). The method was applied to the synthesis of various aromatic amides from aryl iodides and amines, and was scaled to gram order synthesis under as low as 1 atm of carbon monoxide.A mides are very important motifs, found in almost every field of chemistry, in natural products, first and foremost in proteins, but also in various synthetic compounds, from polyamide polymers to various bioactive compounds. In fact, amide formation is the most performed reaction in the pharmaceutical industry, 1 and is also prevalent in other domains such as crop protection. Benzamides and their heteroaromatics relatives account for a large part of those, as displayed in Figure 1.However, amides are notoriously difficult to form. Condensation of acid and amine usually fails to afford more than a few percent of product under extremely harsh conditions. To achieve condensation of those building blocks, activation of the acid by a "coupling reagent" is a usual

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Photoinduced Five‐Component Radical Relay Aminocarbonylation of Alkenes

Lu,

Zhang,

Jiang

et al. 2023

Angewandte Chemie

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Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, and have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled double radical carbonylation reactions has remained a substantial challenge, particularly for the more advanced multi‐component variants, despite their great potential value. Herein, we report a visible light‐driven radical relayed five‐component radical double aminocarbonylation reaction of unactivated alkenes using CO under metal‐free conditions. This protocol provides direct access to valuable γ‐trifluoromethyl α‐ketoamides with good yields and high selectivity. Crucial was the identification of distinct dual roles of amine coupling partners, sequentially acting as electron donors for the formation of photoactive electron donor‐acceptor (EDA) complexes with radical precursors and then as a CO acceptor via nitrogen radical cations to form carbamoyl radicals. Cross‐coupling of carbamoyl radicals with the acyl radicals that are formed in an alkene‐based relay process affords double aminocarbonylation products.

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

Abstract: Radical carbonylation offers potent methods for introducing carbon monoxide into organic molecules. This feature article focuses on our current efforts to develop new strategies for radical carbonylation, which include electron-transfer...

Cited by 9 publications

References 79 publications

Visible light-induced manganese-catalyzed aminocarbonylation of alkyl iodides under atmospheric pressure at room temperature

Visible light-induced manganese-catalyzed aminocarbonylation of alkyl iodides under atmospheric pressure at room temperature

Phosphine-Free Aminocarbonylation Using Pd/DBU Catalyst: Carbonylative Coupling of Aryl Iodides and Amines

Photoinduced Five‐Component Radical Relay Aminocarbonylation of Alkenes

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