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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8270 - 8293

Published: May 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.

Language: Английский

---

Photoredox/NHC cooperative catalysis for alkylacylation of styrenes: An alternative method for the synthesis of γ-aminoketones

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: 156, P. 155450 - 155450

Published: Jan. 8, 2025

Language: Английский

---

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

Molecules, Journal Year: 2024, Volume and Issue: 29(4), P. 790 - 790

Published: Feb. 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.

Language: Английский

---

Phosphonylacylation of Alkenes Enabled by Visible-Light-Induced N-Heterocyclic Carbene Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1711 - 1717

Published: Feb. 20, 2024

Herein, we report the phosphonylacylation of alkenes via visible-light-induced N-heterocyclic carbene (NHC) catalysis to afford a series γ-ketophosphonates in moderate good yields. This protocol features mild conditions, free photocatalyst, and compatibility functional groups. The excited Breslow enolate intermediate was proposed undergo single-electron transfer with oxime phosphonate generate corresponding ketyl radical phosphonyl radical.

Language: Английский

---

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

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13085 - 13092

Published: Aug. 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.

Language: Английский

---

Organocatalytic radical aminoacylation of alkenes for β-aminoketone synthesis

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 14, 2024

Language: Английский

---

Cooperative NHC and Photoredox Catalyzed Radical Aminoacylation of Alkenes to Tetrahydropyridazines

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 27, 2024

Tetrahydropyridazines constitute an important structural motif found in numerous natural products and pharmaceutical compounds. Herein, we report aminoacylation reaction of alkenes that enables the synthesis 1,4,5,6-tetrahydropyridazines through cooperative N-heterocyclic carbene (NHC) photoredox catalysis. This approach involves 6-endo-trig cyclization N-centered hydrazonyl radicals, generated via single-electron oxidation hydrazones, followed by a radical-radical coupling step. The mild process tolerates wide range common functional groups affords variety tetrahydropyridazines moderate to high yields. Preliminary investigations using chiral NHC catalysts demonstrate potential this protocol for asymmetric radical reactions.

Language: Английский

---

Dual N-Heterocyclic Carbene/Photoredox-Catalyzed Coupling of Acyl Fluorides and Alkyl Silanes

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17642 - 17653

Published: Nov. 15, 2024

The combination of N-heterocyclic carbene (NHC) organocatalysis with photochemical activation is becoming increasingly established as an approach for conducting radical organic reactions under mild and practical conditions. As comparatively easy to prepare handle compounds, alkyl silanes are attractive substrates chemistry desilylative mesolysis the corresponding cations known be rapid. Here, we report successful application benzyl silane derivatives source radicals in dual NHC/photoredox-catalyzed radical–radical coupling acyl fluorides. Relatively electron-rich reacted smoothly afford ketones generally good yields, while optimization NHC photocatalyst allowed a wider scope including primary substrates. Furthermore, initial experiments revealed that organosilanes bearing N-, O- S-heteroatoms can also serve sources these

Language: Английский

---