Werner Salt as Nickel and Ammonia Source for Photochemical Synthesis of Primary Aryl Amines DOI

Geyang Song,

Jiameng Song,

Qi Li

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(6)

Published: Nov. 2, 2023

Abstract Cheap, stable and easy‐to‐handle Werner ammine salts have been known for more than a century; but they rarely used in organic synthesis. Herein, we report that the hexammine complex [Ni(NH 3 ) 6 ]Cl 2 can be as both nitrogen catalytic nickel source allow efficient amination of aryl chlorides presence amount bipyridine ligand under irradiation 390–395 nm light without need any additional catalysts. More 80 chlorides, including 20 drug molecules, were aminated, demonstrating practicality generality this method synthetic chemistry. A slow NH release mechanism is operation, obviating problem catalyst poisoning. Still interestingly, show salt easily recovered reused, solving difficult recovery transition metal The protocol thus provides an new strategy synthesis primary amines.

Language: Английский

Modern organic transformations: heterogeneous thermocatalysis or photocatalysis? DOI
Ning Zhang, Wanbing Gong, Yujie Xiong

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review presents the working principles, advantages and disadvantages of heterogeneous thermo- photocatalysis in organic transformations, outlines related applications advancements photocatalytic transformations.

Language: Английский

Citations

0
CsPbBr3 Quantum Dots Promoted Depolymerization of Oxidized Lignin via Photocatalytic Semi‐Hydrogenation/Reduction Strategy DOI
Huating Jiang,

Minxia Liu,

Xiao Lian

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(7)

Published: Jan. 3, 2024

Abstract Due to the demanding depolymerization conditions and limited catalytic efficiency, enhancing lignin valorization remains challenging. Therefore, lowering bond dissociation energy (BDE) has emerged as a viable strategy for achieving mild yet highly effective cleavage of bonds. In this study, photocatalytic semi‐hydrogenation/reduction utilizing CsPbBr 3 quantum dots (CPB‐QDs) Hantzsch ester (HEH 2 ) synergistic system was introduced reduce BDE C β −O−Ar, −O−Ar bond. This offers wide substrate scope encompassing various ‐O‐4 model dimers, preoxidized β‐O‐4 polymers, native oxidized lignin, resulting in production corresponding ketones phenols. Notably, approach attained turnover frequency (TOF) that is 17 times higher than reported Ir‐catalytic dimers. It been observed via meticulous experimentation HEH can be activated by CPB‐QDs single electron transfer (SET), generating ⋅ + hydrogen donor while also serving hole quencher. Moreover, readily forms an active transition state with substrates bonding. Subsequently, proton‐coupled (PCET) from carbonyl group generates α intermediate.

Language: Английский

Citations

2
Metal‐Free Heterogeneous Photocatalysis for Carbocarboxylation of Alkenes: Efficient Synthesis of γ‐Amino Carboxylic Derivatives DOI

Ziwei Wu,

Senmao Zhai,

Meizhen Luo

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(5)

Published: Jan. 18, 2024

Abstract A metal‐free heterogeneous protocol is established herein for the synthesis of value‐added γ‐amino acid scaffolds via carbocarboxylation alkenes with CO 2 and alkylamines under visible light irradiation. The shows broad substrate scope mild reaction conditions good stability catalyst recycle tests. Moreover, methodology could be feasible to late‐stage derivatization several natural products, enriching chemical arsenal practical application.

Language: Английский

Citations

2
Photoredox-Catalyzed Alkene Amination: C(sp2)–H/N–H Radical–Radical Cross Dehydrogenative Coupling DOI
Xiao Chen,

Cailin Ning,

Yating Sui

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2326 - 2331

Published: March 7, 2024

Direct alkene C–H/N–H cross dehydrogenative coupling is an infrequent, highly challenging transformation. Herein, a photoredox radical–radical cross-coupling reaction between ketene dithioacetal as persistent radical cation and azole nitrogen center (NCR) was developed. This direct amination proceeded through synergistic cobalt catalysis, with only H2 evolution. The showed excellent tolerance regio- stereospecific manner, expanding the scope of C(sp2)–N construction methods modes.

Language: Английский

Citations

1
Versatile Quinazolinone Synthesis: N‐Bromosaccharin‐Catalyzed Divergence in 2,3‐Dihydroquinazolin‐4(1H)‐one and Quinazolin‐4(3H)‐one Formation DOI

Samiran Hutait,

Vipin K. Maikhuri,

Avadhesh Kumar Pandey

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(12)

Published: March 19, 2024

Abstract In this research, we present an innovative and eco‐friendly methodology for the synthesis of a diverse array 2,3‐dihydroquinazolin‐4(1H)‐ones, featuring use catalytic N‐Bromosaccharin (NBSac). This novel approach is not limited to just one product; it extends efficient quinazolin‐4(3H)‐ones by harnessing visible light alongside stoichiometric (NBSac) as multifunctional heterogeneous oxidant. By uniting cyclocondensation oxidation into one‐pot sequential process, direct access achieved. The developed protocol characterized its user‐friendliness, metal‐free operation, wide applicability across substrates, ability recycle catalyst, making appealing sustainable method quinazolinone synthesis.

Language: Английский

Citations

1
Photoinduced, Redox-Neutral Decyanative and Defluorinative Phosphination of (Hetero)Arenes DOI

Conghui Wang,

Meizhong Tang,

Yating Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(38), P. 8154 - 8158

Published: Sept. 16, 2024

Triarylphosphines play a crucial role in organic synthesis as versatile components serving ligands, catalysts, and reactants. This study introduces metal-free, visible-light-induced method for the cross-coupling of cyanopyridines or polyfluoroarenes with diarylphosphines. approach facilitates formation C(sp

Language: Английский

Citations

1
Amine‐Free, Directing‐Group‐Free and Redox‐Neutral α‐Alkylation of Saturated Cyclic Ketones DOI

Jia Qiao,

Rui‐Nan Ci,

Qi‐Chao Gan

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(29)

Published: May 23, 2023

Abstract The activation of the α‐C−H bond ketones typically requires an amine and a directing group to guide reaction selectivity in amine‐catalysis carbonyl chemistry. For ketone, groups are also required control selectivity. Reported herein is first α‐alkylation cyclic absence catalyst group. 1 H NMR, XPS, EPR studies DFT calculations indicate that α‐carbon radical intermediate formed through direct selective inert chelating on surface colloidal quantum dots (QDs). Such interaction essential for weakening C−H bond, as exemplified, using CdSe QDs sole photocatalyst execute alkylation under visible‐light irradiation. Without group, high step‐ atom‐economy transformation redox‐neutral condition opens new way functionalization

Language: Английский

Citations

3
Visible light-induced C(sp3)–H azolation of ethers via radical-polar crossover DOI
Cheng Huang,

Yu-Shu Qin,

Chen-Lu Wang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(19), P. 2669 - 2672

Published: Jan. 1, 2024

We report a metal-free and photocatalyst-free strategy for C(sp 3 )–H azolation of ethers via hydrogen-atom transfer radical-polar crossover process.

Language: Английский

Citations

0
Quantitative Evaluation of a Quasi-Fermi Level of the Hole at a Photoanode/Electrolyte Interface DOI Creative Commons
Kazuhiro Takanabe,

Yuu Shioiri,

Keisuke Obata

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Sept. 7, 2023

Abstract Valence band maximum (VBM) position does not necessarily indicate the driving force for oxidation reactions on photoanodes because it simply reflects an electrostatic potential. Rather, quasi-Fermi level of hole at surface must be considered. Here, we report a protocol to quantitatively evaluate holes using redox species with various potentials. The these is estimated by correlating photocurrent derived from separately measured electrode potential stable model glassy carbon electrode. Using this protocol, levels CdS and CdSe were found limited merely 0.5 V vs. standard hydrogen electrode; fairly negative VBM position. estimation partial density photocorrosion further enabled predictions kinetics. predicted kinetics showed that are pinned facile photocorrosion. This methodology offers quantitative understanding capability photoanodes.

Language: Английский

Citations

1
Werner Salt as Nickel and Ammonia Source for Photochemical Synthesis of Primary Aryl Amines DOI

Geyang Song,

Jiameng Song,

Qi Li

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(6)

Published: Nov. 2, 2023

Abstract Cheap, stable and easy‐to‐handle Werner ammine salts have been known for more than a century; but they rarely used in organic synthesis. Herein, we report that the hexammine complex [Ni(NH 3 ) 6 ]Cl 2 can be as both nitrogen catalytic nickel source allow efficient amination of aryl chlorides presence amount bipyridine ligand under irradiation 390–395 nm light without need any additional catalysts. More 80 chlorides, including 20 drug molecules, were aminated, demonstrating practicality generality this method synthetic chemistry. A slow NH release mechanism is operation, obviating problem catalyst poisoning. Still interestingly, show salt easily recovered reused, solving difficult recovery transition metal The protocol thus provides an new strategy synthesis primary amines.

Language: Английский

Citations

1