Radical Reactions with N-Heterocyclic Carbene (NHC)-Derived Acyl Azoliums for Access to Multifunctionalized Ketones

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8270 - 8293

Опубликована: Май 13, 2024

As one of the most important key intermediates, NHC-bound acylazolium-based ionic transformations have been intensively explored in past two decades. With expeditious development NHC-catalyzed radical recent years, acylazolium chemistry has reached another level, with number relevant publications increasing significantly. However, a summary focused on acylations NHC-derived acyl azoliums classified according to mechanistic difference not reported. Such detailed classification and deep analysis provide opportunities for better understanding history trend this field. In review, reactions N-heterocyclic carbene (NHC)-derived are systematically introduced. The achievements challenges within area also summarized discussed at end.

Язык: Английский

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Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(21), С. 14745 - 14753

Опубликована: Май 14, 2024

We herein describe a Ni-catalyzed formal hydroamidation of readily available α,β-unsaturated carbonyl compounds to afford valuable chiral β-amino acid derivatives (up >99:1 e.r.) using dioxazolones as robust amino source. A wide range alkyl-substituted olefins conjugated esters, amides, thioesters, and ketones were successfully amidated at the β-position with excellent enantioselectivity for first time. Combined experimental computational mechanistic studies supported our working hypothesis that this unconventional β-amidation unsaturated substrates can be attributed polar-matched migratory olefin insertion an (amido)(Cl)Ni

Язык: Английский

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Visible light-mediated organocatalyzed 1,3-aminoacylation of cyclopropane employing N-benzoyl saccharin as bifunctional reagent

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Окт. 16, 2024

The carboamination of unsaturated molecules using bifunctional reagents is considered an attractive approach for the synthesis nitrogen-containing compounds. However, C-N have never been employed in cyclopropane. In this study, we use N-heterocyclic carbene (NHC), N-benzoyl saccharin, as a reagent and photoredox catalyst dual-catalyzed 1,3-aminoacylation NHCs play multiple roles, functioning Lewis base catalysts to activate bonds, promoting oxidative quenching process PC*, acting efficient acyl radical transfer formation C-C bonds. between excited-state PC* NHC adduct key photooxidation generality aryl cyclopropanes.

Язык: Английский

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C(sp³)–H Carboxylation via Carbene/Photoredox Cooperative Catalysis

ACS Catalysis, Год журнала: 2025, Номер 15(2), С. 1287 - 1293

Опубликована: Янв. 7, 2025

C(sp3)–H bond functionalization is a powerful strategy for the synthesis of organic compounds due their abundance in simple starting materials. Photoredox catalysis has led to diverse array enabling activation strategies; however, general platform direct carboxylic acid derivatives remains elusive. Disclosed herein development cooperative NHC/photoredox-catalyzed esterification transformation. This method enables access benzylic, α-heteroatom, and formal β-esterification products moderate high yields under mild reaction conditions.

Язык: Английский

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Copper-Catalyzed Selective Amino-alkoxycarbonylation of Unactivated Alkenes with CO

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction different functional groups and rapid construction valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation unactivated with CO alkylamine precursors in presence Lewis acid additive. The novel protocol allows direct access to β-amino derivatives from easily available starting materials. presented methods feature high chemo- regioselectivities, good group tolerance, substrate scope including diverse bioactive compounds drug-like molecules. Mechanistic studies indicate that additive is key realizing umpolung addition nucleophilic aminyl radicals electron-rich alkenes, which represents an elegant activation strategy for radicals.

Язык: Английский

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Development of Cytolytic Iridium-Complexed Octaarginine Peptide Albumin Nanomedicine for Hepatocellular Carcinoma Treatment

International Journal of Nanomedicine, Год журнала: 2025, Номер Volume 20, С. 2395 - 2409

Опубликована: Фев. 1, 2025

Hepatocellular carcinoma is one of the most challenging malignancies and has high incidence mortality rates worldwide. Digital subtraction angiography (DSA)-guided hepatic arterial infusion standard chemotherapeutic agent oxaliplatin (OXA) advantages both precision efficacy, making it an important therapeutic strategy for advanced-stage liver cancer. However, patients receiving this treatment still face severe systemic toxicity poor tolerability oxaliplatin. In study, we compared with novel albumin-formulated oncolytic peptide nanoparticles, Ir-cR8 (abbreviated as iPep), in orthotopic cancer a mouse model by intravenous injection rabbit via DSA-guided infusion. The results showed that Ir-cR8-BSA-NPs had enhanced inhibitory effects to growth H22 ectopic tumors mice also reduced animals OXA treatment. Specifically, Ir-cR8-BSA-NPs-treated approximately 92% tumor inhibition 88% OXA. VX2 hepatocellular model, demonstrated significantly stronger (P<0.01) size OXA, assessed PET/CT imaging, SUV values decreasing from 5.15±0.46 2.52±0.57, OXA-treated group, which decreased 5.44±0.43 3.90±0.24. Furthermore, Ir-cR8- BSA-NPs improved stability albumin encapsulation hemolytic (P<0.001), resulting efficacy. This study combined membrane-active nanomedicine precise drug delivery enabled technology interventional

Язык: Английский

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Visible Light-Mediated Monofluoromethylation/Acylation of Olefins by Dual Organo-Catalysis

Molecules, Год журнала: 2024, Номер 29(4), С. 790 - 790

Опубликована: Фев. 8, 2024

Monofluoromethyl (CH2F) motifs exhibit unique bioactivities and are considered privileged units in drug discovery. The radical monofluoromethylative difunctionalization of alkenes stands out as an appealing approach to access CH2F-containing compounds. However, this strategy remains largely underdeveloped, particularly under metal-free conditions. In study, we report on visible light-mediated three-component monofluoromethylation/acylation styrene derivatives employing NHC organic photocatalyst dual catalysis. A diverse array α-aryl-β-monofluoromethyl ketones was successfully synthesized with excellent functional group tolerance selectivity. mild CH2F generation from NaSO2CFH2 holds potential for further applications fluoroalkyl chemistry.

Язык: Английский

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Photoredox/NHC Dual Catalysis Enabled de Novo Synthesis of α-Amino Acids Derivatives

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 23, 2024

Herein, we report a mild and operationally simple photoredox/NHC dual catalysis strategy for the α-carboxylation of tertiary amine C(sp

Язык: Английский

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1,2-Amidoarylcarbonylation of Styrenes to Access β-Acylamino Ketones by NHC-Catalyzed Radical Relay

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13085 - 13092

Опубликована: Авг. 28, 2024

An amidoarylcarbonylation reaction of aromatic aldehydes and olefins with Katritzky pyridinium salts by N-heterocyclic carbene (NHC)-catalyzed radical relay to construct C-C C-N bonds good functional group tolerance is developed for the synthesis β-acylamino ketones. This gentle efficient approach offers a valuable style Mechanistic studies revealed that addition/coupling/elimination cascade process was involved in this reaction.

Язык: Английский

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Light-Driven N-Heterocyclic Carbene-Catalyzed Multi-Component Reaction for the Synthesis of β-Amino Ketones

Organic Letters, Год журнала: 2024, Номер 26(41), С. 8848 - 8853

Опубликована: Окт. 8, 2024

A N-heterocyclic carbene-catalyzed (NHC) three-component reaction involving

Язык: Английский

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