A Benzophenothiazine/Boronic Acid Hybrid Photocatalyst Enables the Single Electron Transfer (SET) to Carboxy Groups: SET-Initiated Cyclization of α,β-Unsaturated Carboxylic Acids DOI

Taichi Yumura,

Takeshi Nanjo, Yoshiji Takemoto

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12803 - 12809

Published: Sept. 18, 2023

In this article, we report an efficient hybrid photoredox catalyst that combines N-arylbenzophenothiazine and a boronic acid. The forms complex with the substrate to enable single electron reduction of redox-inactive carboxy groups under visible-light irradiation. Via approach, two types radical cyclization α,β-unsaturated carboxylic acids previously required harsh reaction conditions can be achieved, i.e., [2 + 2] cycloaddition reductive cyclization. Mechanistic studies have revealed photocatalyst promotes transfer toward generally unreactive cyclobutane acid moieties adducts as well acids, leading unusual cis–trans isomerization rings via reversible ring-opening/-closing process.

Language: Английский

Electrophotocatalytic hydrogenation of imines and reductive functionalization of aryl halides DOI Creative Commons
Wenjie Kang, Yanbin Zhang, Bo Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 22, 2024

Abstract The open-shell catalytically active species, like radical cations or anions, generated by one-electron transfer of precatalysts are widely used in energy-consuming redox reactions, but their excited-state lifetimes usually short. Here, a closed-shell thioxanthone-hydrogen anion species ( 3 ), which can be photochemically converted to potent and long-lived reductant, is under electrochemical conditions, enabling the electrophotocatalytic hydrogenation. Notably, TfOH regulate potential this system. In presence TfOH, precatalyst 1 ) reduction occur at low potential, so that competitive H 2 evolution inhibited, thus effectively promoting hydrogenation imines. absence reducing ability system reach potency even comparable Na 0 Li , thereby allowing hydrogenation, borylation, stannylation (hetero)arylation aryl halides construct C−H, C−B, C−Sn, C−C bonds.

Language: Английский

Citations

18
Recent Advances in Deuteration Reactions† DOI
Hao Li, Shabbir Muhammad, Wu Li

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(10), P. 1145 - 1156

Published: Dec. 26, 2023

Comprehensive Summary The deuteration of organic compounds has attracted more attentions in recent years for the potential applications new drug discovery and synthetic chemistry. For this purpose, many efficient deuterium labeling methodologies have been developed, including hydrogen isotope exchange (HIE), reductive deuteration, dehalogenative that allow synthesis selectively deuterated compounds. In last few years, great breakthroughs selective achieved interest molecules is rising. review, we summarized developments since 2021. Several types key processes incorporation reactions, H/D exchange, are introduced discussed. Key Scientists 2000s, Derdau Atzrodt's group made contributions to directing assisted noble‐metal catalyzed arenes labeled During same period, Sajiki co‐workers completed a series reactions by heterogeneous platinum‐group metal catalysts. Since 2015, Gregory Pieters developed ruthenium catalysts exchange. 2016, Chirik's presence homogeneous iron complex. David MacMillan coworkers photocatalyzed HIE α‐amino C(sp 3 )–H bonds. From 2020, nanoelectrodes were designed deuterations unactivated unsaturated bonds Zhang's group. Recently, Beller's several strategies isotopic using earth‐abundant Our review latest important

Language: Английский

Citations

29
Confinement of p‐Xylene in the Pores of a Bilanthanide Metal–Organic Framework for Highly Selective Recognition DOI Open Access
Mengmeng Wang, Zongsu Han, Kunyu Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 13, 2023

The rapid and accurate sensing of p-xylene, an essential raw material with a multi-billion-dollar market, in xylene mixture is great significance industry; however, the highly similar molecular structures, energy levels, spectral characteristics isomers make selective recognition extremely challenging. Metal-organic frameworks (MOFs) exhibiting tailorable pores potential binding sites provide prospects for but comprehensive understanding pore effect still elusive, primarily due to intricacies involved process. Herein, we reported robust bilanthanide MOF NKU-999-EuTb precisely engineered accommodate which were confirmed by single crystal X-ray diffraction dynamic magnetic susceptibilities. exhibits high-performance p-xylene towards its isomers. Through systematical study, it was revealed that absorbing into governs performance. This work provides insights developing advanced materials complex

Language: Английский

Citations

19
Reductive Cross-Coupling of Olefins via a Radical Pathway DOI Creative Commons
Wei Zhou, Igor A. Dmitriev, Paolo Melchiorre

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(46), P. 25098 - 25102

Published: Nov. 10, 2023

Olefins are widely available at low costs, which explains the usefulness of developing new methods for their functionalization. Here we report a simple protocol that uses photoredox catalyst and an inexpensive thiol to stitch together two olefins, forming C-C bond. Specifically, electron-poor olefin is reduced by generate, upon protonation, carbon radical, then captured neutral olefin. This intermolecular cross-coupling process provides tool rapidly synthesizing sp3-dense molecules from olefins using unconventional disconnection.

Language: Английский

Citations

16
Generation of Thioxanthone Hydrogen Anion by Double Photoreduction and Uses for Catalytic Photoreductions DOI
Wenjie Kang, Bo Li, Zijian Zhao

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13588 - 13596

Published: Oct. 9, 2023

Anions are the reduced form of precatalysts that a special type photoredox catalyst, unlike traditional iridium or ruthenium complexes. Among them, radical anions often have much shorter excited-state lifetimes because fast nonradiative decay. Herein, we report discovery thioxanthone hydrogen anion (5), super-reducing photocatalyst with long lifetime (Eox* = −2.74 V vs SCE, τS 4.1 ns). Using 5 as catalytic reductant, developed series photoreductions, including hydrogenation, reductive dehalogenation, deoxygenative and deoxygenation, thereby demonstrating feasibility 2e– consecutive photoinduced electron transfer (ConPET) strategy versatility catalyst.

Language: Английский

Citations

11
Oxidative cross-coupling of quinoxalinones with indoles enabled by acidochromism DOI
Jie Huang, Long Wang, Xiang‐Ying Tang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(13), P. 2709 - 2714

Published: Jan. 1, 2023

We report a new gate for changing photo inactive compounds into photocatalysts with easy operation, good tolerance of functional groups, and considerable yield. demonstrate the synthesis natural products Azacephalandole A Cephalandole in high yields.

Language: Английский

Citations

10
Visible-Light-Induced Imine Hydrogenation Catalyzed by Thioxanthone-TfOH Complex DOI

Shijie Sun,

Jiahong Wang, Hao Guo

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Amino compounds are important molecules, commonly found in nature and widely applied industrial production. Recently, photocatalysis has been discovered as an efficient method to synthesize amino by promoting imine hydrogenation. In this work, a strategy of hydrogenation catalyzed 2e– consecutive photoinduced electron transfer (ConPET) process thioxanthone-TfOH complex (9-HTXTF) was thoroughly investigated with its reaction conditions optimized, substrate scope examined, mechanism elucidated, which provides for synthesizing compounds.

Language: Английский

Citations

0
Visible Light-Induced Divergent Deoxygenation/Hydroxymethylation of Pyridine N-Oxides DOI
Changhao Feng, Hao Guo, Aishun Ding

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

This study explores the deoxygenation of pyridine N-oxides and presents a one-step photoredox method for direct synthesis 2-hydroxymethylated pyridines from N-oxides. Mechanism studies elucidate role catalyst provide evidence possible electron transfer process formation key radicals. A range derivatives, particularly 2-hydroxymethyl-substituted pyridines, which may be difficult to obtain, can synthesized in single step.

Language: Английский

Citations

0
Dual anion and cation catalysis enabled by an ion-pairing photocatalyst DOI

Xi-Xian Chen,

Xiang Chen,

Feng Lan

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A dual catalysis involving both anionic and cationic species of an ion-pairing photocatalyst is achieved. By adopting this mode action, photocatalytic hydrogen transfer cross-coupling reactions can be enabled using a single photocatalyst.

Language: Английский

Citations

0
Highly selective 1,4-hydrogenation of conjugated dienes by photoinduced electron transfer and proton transfer DOI Creative Commons
Changhao Feng, Jiahong Wang, Hao Guo

et al.

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: unknown, P. 102561 - 102561

Published: April 1, 2025

Language: Английский

Citations

0