Dual N-Heterocyclic Carbene/Photoredox-Catalyzed Coupling of Acyl Fluorides and Alkyl Silanes DOI Creative Commons
Michael Jakob, Luca Steiner,

Marius Göbel

et al.

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

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

Hui Cai,

Xiaoqun Yang,

Shi‐Chao Ren

et al.

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

Citations

23
Energy-Transfer-Enabled Radical Acylation Using Free Alkyl Boronic Acids through Photo and NHC Dual Catalysis DOI

Wan-Cong Liu,

Xiang Zhang, Lin Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3181 - 3190

Published: Feb. 14, 2024

Cross-coupling reactions have been well received as one of the most popular protocols for ketone synthesis. As an important coupling partner, bench-stable and commercially available alkyl boronic acids are widely used in transition metal catalysis, but they rarely utilized radical precursors acylative reactions. Herein, we reported energy-transfer-enabled acylation using free via NHC/photo dual catalysis. This protocol could efficiently promote Suzuki-type cross-coupling between acyl imidazoles multicomponent alkylacylations alkenes, thus producing various ketones with structural diversity. Additionally, products can readily transform into a large number structurally interesting fine chemicals. Preliminary mechanistic studies shed light on unique reaction mechanism.

Language: Английский

Citations

10
N-heterocyclic carbene and photocatalyst-catalyzed rapid access to indole ketones via radical C(sp3)–H acylation DOI

Guihua Nie,

Ting Tu,

Tianhui Liao

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(9), P. 5397 - 5408

Published: Jan. 1, 2024

Carbene and photocatalyst-catalyzed rapid access to indole ketones via radical C(sp 3 )–H acylation.

Language: Английский

Citations

5
Synthesis of γ-Oxo-phosphonates via N-Heterocyclic Carbene-Catalyzed Acylphosphorylation of Alkenes DOI

Jia‐Nan Mo,

Shengbin Sun,

Huiwei Xu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2197 - 2201

Published: March 7, 2024

In this study, we present an N-heterocyclic carbene-catalyzed method for the radical acylphosphorylation of alkenes. Electrochemical investigations were employed to identify appropriate class oxime phosphonates capable undergoing a single-electron transfer (SET) with Breslow enolates. The resulting phosphoryl radicals effectively coupled diverse styrenes and aldehydes yield variety γ-oxo-phosphonates. Both clock experiments electrochemical studies support our reaction design, plausible mechanism organocatalytic transformation is proposed.

Language: Английский

Citations

4
Phosphonylacylation of Alkenes Enabled by Visible-Light-Induced N-Heterocyclic Carbene Catalysis DOI

Ming‐Lei Jin,

Yi-Xiong Dong,

Zhong‐Hua Gao

et al.

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

Citations

3
Stereoselective Radical Acylfluoroalkylation of Bicyclobutanes via N‐Heterocyclic Carbene Catalysis DOI

Chuyu Xiao,

Jing‐Ran Shan,

Wen‐Deng Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 14, 2024

Cyclobutanes are prominent structural components in natural products and drug molecules. With the advent of strain-release-driven synthesis, ring-opening reactions bicyclo[1.1.0]butanes (BCBs) provide an attractive pathway to construct these three-dimensional structures. However, stereoselective difunctionalization central C-C σ-bonds remains challenging. Reported herein is a covalent-based organocatalytic strategy that exploits radical NHC catalysis achieve diastereoselective acylfluoroalkylation BCBs under mild conditions. The Breslow enolate acts as single electron donor provides NHC-bound ketyl with appropriate steric hindrance, which effectively distinguishes between two faces transient cyclobutyl radicals. This operationally simple method tolerates various fluoroalkyl reagents common functional groups, providing straightforward access polysubstituted cyclobutanes (75 examples, up >19 : 1 d.r.). combined experimental theoretical investigations this system confirm formation NHC-derived understanding how radical-radical coupling occurs.

Language: Английский

Citations

3
Synthesis of Pyrroloindolines via N-Heterocyclic Carbene Catalyzed Dearomative Amidoacylation of Indole Derivatives DOI

Hanyu Shu,

Jia‐Nan Mo,

Wen-Deng Liu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(48), P. 8677 - 8682

Published: Nov. 23, 2023

Pyrroloindoline is a privileged heterocyclic motif that widely present in many natural products and pharmaceutical compounds. Herein, we report an amidyl radical-mediated dearomatization for synthesizing series of pyrroloindolines via N-heterocyclic carbene catalysis. In this organocatalytic process, the Breslow enolate served as both single electron donor acyl radical equivalent to assemble C3a-acyl with broad substrate scope. Sequential reduction indole derivatives provided analogues (±)-desoxyeseroline, which exhibited potential anticancer activity.

Language: Английский

Citations

9
Redox-Paired Reductive Heck Reaction and Oxidative Esterification Catalyzed by Mesoionic Carbenes DOI

B. HUANG,

Zengyu Zhang, J. B. Jiao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7419 - 7424

Published: Aug. 22, 2024

Paring a reductive reaction and an oxidative in one could be immensely important achieving atom economic environmental advantages. Herein, we report simple protocol that combines two such Heck reactions esterification by using mesoionic carbenes as catalysts to synthesize multiple valuable products under mild conditions.

Language: Английский

Citations

2
Organocatalytic radical aminoacylation of alkenes for β-aminoketone synthesis DOI

Ayisenbati Jialingbieke,

Xinying Hu,

Z. Liu

et al.

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

Published: Oct. 14, 2024

Language: Английский

Citations

2
Cooperative NHC and Photoredox Catalyzed Radical Aminoacylation of Alkenes to Tetrahydropyridazines DOI

Wen‐Deng Liu,

Jiyuan Gao,

Jia‐Nan Mo

et al.

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

Citations

0