Cooperative Photoredox and N-Heterocyclic Carbene Catalysis Suzuki–Miyaura-Type Reaction: Radical Coupling of Aroyl Fluorides and Alkyl Boronic Acids DOI

Shihao Li,

Chaoyang Zhang, Sheng Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1728 - 1733

Published: Feb. 22, 2024

An intermolecular Suzuki–Miyaura-type reaction of benzoyl fluorides with alkyl boronic acids to synthetic ketone was revealed by cooperative N-heterocyclic carbene (NHC) and photoredox catalysis. Various boric can be converted into radicals without external oxidants or activators. Moreover, the catalytic system feasible for difunctionalization styrenes via a radical relay process. Mechanistic experiments suggested that benzoate anion intermediate might play unique role in this system.

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

25

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

Homologation of Ketones: Direct Transformation of Alkyl Ketones to Aryl Ketones via Photoredox Catalyzed Deacylation-Aroylation Sequence DOI
Tian Wang, Zengyu Zhang, Fan Gao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6915 - 6920

Published: Aug. 8, 2024

Ketones, as essential functional group skeletons, have garnered significant interest due to their diverse transformations. Herein, we describe a versatile photoredox catalyzed deacylation-aroylation strategy that enables the direct transformation of alkyl ketones aryl ketones. This process involves deacylation dihydroquinazolinones derived from generate radicals, followed by subsequent NHC-catalyzed or NHC-mediated radical aroylation.

Language: Английский

Citations

10

Engineering Single Cu Atoms Anchored via N‐Heterocyclic Carbene in COF Mesopores for Modulating Electron Kinetics of CO2 Photoconversion DOI
Zhongyu Liu,

Haochun Yin,

Jianhui Sun

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: unknown

Published: June 9, 2024

Abstract Charge transfer and carbon dioxide (CO 2 ) adsorption/activation are critical factors for the electron kinetics during CO photoconversion. Herein, high‐loading robust single Cu atoms (7.8 wt.%) anchored via N‐heterocyclic carbene ligands derived from imidazolium ionic liquid motifs, precisely bonding to acceptors of mesoporous donor‐acceptor pyridine‐covalent organic framework (pCOF) nanosheets. By engineering valance coordination structure, atomic Cu(I)‐CO sites, superior Cu(II)‐CN OCl ones, enable a 22‐fold increase conversion rate compared pCOF in pure water, ≈100% selectivity toward CO, an apparent quantum yield 1.7% (420 nm). The photoactivity outperforms analogous COF‐based photocatalysts under similar conditions. Experimental results prove Cu(I) possess more improved capture capacities than Cu(II) ones. Combining fs‐ µs‐transient absorption spectroscopy, mechanism is investigated on single‐atom photocatalyst model. fs‐transient spectra confirm can rapidly extract electrons electron‐rich region along carbene, exhibiting 3 × 10 9 s −1 . Using situ efficiency quantified reach 60.4% photocatalytic reaction This work provides rational design strategy advanced photocatalysts.

Language: Английский

Citations

7

N -Heterocyclic carbene catalytic 1,2-boron migrative acylation accelerated by photocatalysis DOI Creative Commons
Huang Hua, Zhaoyuan Yu,

Luyao Han

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(30)

Published: July 24, 2024

The transformation of organoboron compounds plays an important role in synthetic chemistry, and recent advancements boron-migration reactions have garnered considerable attention. Here, we report unprecedented 1,2-boron migrative acylation upon photocatalysis-facilitated

Language: Английский

Citations

7

Lateral nanoarchitectonics from nano to life: Ongoing challenge in interfacial chemical science DOI Creative Commons
Jingwen Song, Anna Jančík Procházková, Kohsaku Kawakami

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(45), P. 18715 - 18750

Published: Jan. 1, 2024

The construction of functional structures within a single plane still has lot challenges. This review article will help us find new groundbreaking directions in lateral nanoarchitectonics toward advanced material organization.

Language: Английский

Citations

7

NHC-mediated photocatalytic para-selective C–H acylation of aryl alcohols: regioselectivity control via remote radical spiro cyclization DOI

Tinglei Zhang,

Lei Wang,

Xiaolin Peng

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Language: Английский

Citations

1

NHC and photoredox catalysis dual-catalyzed 1,4-mono-/di-fluoromethylative acylation of 1,3-enynes DOI

Jiuli Xia,

Ruiyang Ma,

Lihong V. Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3089 - 3099

Published: Jan. 1, 2024

NHC and photocatalysis dual-catalyzed mono/difluoromethylative acylation of 1,3-enynes was realized, providing fluormethyl-substituted allenyl ketones. SO 2 might play a critical role in achieving high reactivity selectivity.

Language: Английский

Citations

5

Electron-Donor-Mediated Divergent Transformation of Br–RF via EDA Complex for the Synthesis of Fluorine-Containing Oxindoles and Amides DOI
Shupeng Zhang,

Jin-Xin Lan,

Mei-Ling Yang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 9990 - 9995

Published: Nov. 11, 2024

We have developed an unprecedented electron-donor-controlled divergent reaction between

Language: Английский

Citations

5

Radical Acylfluoroalkylation of 1,3-Enynes via N-Heterocyclic Carbene/Photoredox Cooperative Catalysis DOI
Shichao Tian, Ning Chen, Keguang Cheng

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4351 - 4355

Published: May 10, 2024

We report a novel three-component radical acylfluoroalkylation of 1,3-enynes by synergistic N-heterocyclic carbene (NHC)/photoredox catalysis toward various fluorinated allenic aryl ketones. This protocol features broad substrate scope and excellent functional group tolerability, with examples late-stage modification drug molecules natural products. Notably, seven different fluoroalkyl motifs can be introduced to 1,3-enynes, further demonstrating the robustness generality this method. The generation from each sulfinate reagent was individually supported EPR experiments.

Language: Английский

Citations

4