Search Results (16)

Fluorinated organic molecules have become indispensable in modern chemistry, owing to the unique properties imparted by fluorine to other compounds, including enhanced metabolic stability, controlled lipophilicity, and improved bioavailability. The site-selective incorporation of fluorine atoms into organic frameworks is essential in pharmaceutical, agrochemical, and material science research. In recent years, catalytic fluorination has become an important methodology for the efficient and selective incorporation of fluorine atoms into complex molecular architectures. This review highlights advances in catalytic fluorination reactions over the past six years and describes the contributions of transition metal catalysts, photocatalysts, organocatalysts, and electrochemical systems that have enabled site-selective fluorination under a variety of conditions. Particular attention is given to the use of well-defined fluorinating agents, including Selectfluor, N-fluorobenzenesulfonimide (NFSI), AlkylFluor, Synfluor, and hypervalent iodine reagents. These reagents have been combined with diverse catalytic systems, such as AgNO₃, Rh(II), Mo-based complexes, Co(II)-salen, and various organocatalysts, including β,β-diaryl serine catalysts, isothiourea catalysts, and chiral phase-transfer catalysts. This review summarizes proposed mechanisms reported in the original studies and discusses examples of electrophilic, nucleophilic, radical, photoredox, and electrochemical fluorination pathways. Recent developments in stereoselective and more sustainable protocols are also examined. By consolidating these strategies, this article provides an up-to-date perspective on catalytic fluorination and its impact on synthetic organic chemistry. Full article

Porphyrins were identified some years ago as a promising, easily accessible, and tunable class of organic photoredox catalysts, but a systematic study on the effect of the electronic nature and of the position of the substituents on both the ground-state and the excited-state redox potentials of these compounds is still lacking. We prepared a set of known functionalized porphyrin derivatives containing different substituents either in one of the meso positions or at a β-pyrrole carbon, and we determined their ground- and (singlet) excited-state redox potentials. We found that while the estimated singlet excited-state energies are essentially unaffected by the introduction of substituents, the redox potentials (both in the ground- and in the singlet excited-state) depend on the electron-withdrawing or electron-donating nature of the substituents. Thus, the presence of groups with electron-withdrawing resonance effects results in an enhancement of the reduction facility of the photocatalyst, both in the ground and in the excited state. We next prepared a second set of four previously unknown meso-substituted porphyrins, having a benzoyl group at different positions. The reduction facility of the porphyrin increases with the proximity of the substituent to the porphine core, reaching a maximum when the benzoyl substituent is introduced at a meso position. Full article

The oxidation of benzylic alcohols is an important transformation in modern organic synthesis. A plethora of photoredox protocols have been developed to achieve the aerobic oxidation of alcohols into carbonyls. Recently, several groups described that ultraviolet (UV) or purple light can initiate the aerobic oxidation of benzylic alcohols in the absence of an external catalyst, and depicted different mechanisms involving the photoinduction of ^•O₂⁻ as a critical reactive oxygen species (ROS). However, based on comprehensive mechanistic investigations, including control experiments, radical quenching experiments, EPR studies, UV–vis spectroscopy, kinetics studies, and density functional theory calculations (DFT), we elucidate here that HOO^•, which is released via the H₂O₂ elimination of α-hydroxyl peroxyl radicals [ArCR(OH)OO^•], serves as the real chain carrier for the autocatalytic photooxidation of benzylic alcohols. The mechanistic ambiguities depicted in the precedent literature are clarified, in terms of the crucial ROS and its evolution, the rate-limiting step, and the primary radical cascade. This work highlights the necessity of stricter mechanistic analyses on UV-driven oxidative reactions that involve aldehydes’ (or ketones) generation. Full article

A novel and efficient method for functionalizing organosulfones has been established, utilizing a visible-light-driven intermolecular radical cascade cyclization of α-allyl-β-ketosulfones. This process employs fac-Ir(ppy)₃ as the photoredox catalyst and α-carbonyl alkyl bromide as the oxidizing agent. Via this approach, the substrates experience intermolecular addition of α-carbonyl alkyl radicals to the alkene bonds, initiating a sequence of C-C bond formations that culminate in the production of organosulfone derivatives. Notably, this technique features gentle reaction conditions and an exceptional compatibility with a wide array of functional groups, making it a versatile and valuable addition to the field of organic synthesis. Full article

Photoinduced metal-free ATRP has been successfully applied to fabricate thermo-responsive cellulose graft copolymer (PNIPAM-g-Cell) using 2-bromoisobuturyl bromide-modified cellulose as the macroinitiator. The polymerization of N-isopropylacrylamide (NIPAM) from cellulose was efficiently activated and deactivated with UV irradiation in the presence of an organic-based photo-redox catalyst. Both FTIR and ¹³C NMR analysis confirmed the structural similarity between the obtained PNIPAM-g-Cell and that synthesized via traditional ATRP methods. When the concentration of the PNIPAM-g-Cell is over 5% in water, it forms an injectable thermos-responsive hydrogel composed of micelles at 37 °C. Since organic photocatalysis is a metal-free ATRP, it overcomes the challenge of transition-metal catalysts remaining in polymer products, making this cellulose-based graft copolymer suitable for biomedical applications. In vitro release studies demonstrated that the hydrogel can continuously release DOX for up to 10 days, and its cytotoxicity indicates that it is highly biocompatible. Based on these findings, this cellulose-based injectable, thermo-responsive drug-loaded hydrogel is suitable for intelligent drug delivery systems. Full article

Carbon dioxide is ideal for carboxylation reactions as a renewable and sustainable C1 feedstock and has significant recognition owing to its low cost, non-toxicity, and high abundance. To depreciate the environmental concentration of CO₂, which causes the greenhouse gas effect, developing new catalytic protocols for organic synthesis in CO₂ utilization is of great importance. This review focuses on carboxylation reactions using CO₂ as a C1 feedstock to synthesize value-added functionalized carboxylic acids and their corresponding derivatives via catalytically generated allyl metal intermediates, photoredox catalysis, and electrocatalysis with a focus on recent developments and opportunities in catalyst design for carboxylation reactions. In this article, we describe recent developments in the carboxylation of C–H bonds, alkenes, and alkynes using CO₂ as the C1 source for various reactions under different conditions, as well as the potential direction for the further development of CO₂ utilization in organic synthesis. Full article

TiO₂ is one of the most promising heterogeneous photoredox catalysts employed in oxidative pollutant destruction, CO₂ reduction, water splitting, disinfection, solar cell design and organic synthesis. Due to the wide bandgap of TiO₂, visible light energy is not sufficient for its activation, and electron/hole pairs generated upon UV irradiation demonstrate limited selectivity for application in organic synthesis. Thus, the development of TiO₂-based catalytic systems activated by visible light is highly attractive. In the present work we demonstrate the generation of t-BuOO• radicals from tert-butylhydroperoxide catalyzed using commercially available unmodified TiO₂ under visible light. This finding was used for the highly selective CH-peroxidation of barbituric acids, which contrasts with the behavior of the known TiO₂/H₂O₂/UV photocatalytic system used for deep oxidation of organic pollutants. Full article

Synthetic organic pigments from the direct discharge of textile effluents are considered as colossal global concern and attract the attention of scholars. The efficient construction of heterojunction systems involving precious metal co-catalysis is an effective strategy for obtaining highly efficient photocatalytic materials. Herein, we report the construction of a Pt-doped BiFeO₃/O-g-C₃N₄ (Pt@BFO/O-CN) S-scheme heterojunction system for photocatalytic degradation of aqueous rhodamine B (RhB) under visible-light irradiation. The photocatalytic performances of Pt@BFO/O-CN and BFO/O-CN composites and pristine BiFeO₃ and O-g-C₃N₄ were compared, and the photocatalytic process of the Pt@BFO/O-CN system was optimized. The results exhibit that the S-scheme Pt@BFO/O-CN heterojunction has superior photocatalytic performance compared to its fellow catalysts, which is due to the asymmetric nature of the as-constructed heterojunction. The as-constructed Pt@BFO/O-CN heterojunction reveals high performance in photocatalytic degradation of RhB with a degradation efficiency of 100% achieved after 50 min of visible-light irradiation. The photodegradation fitted well with pseudo-first-order kinetics proceeding with a rate constant of 4.63 × 10⁻² min⁻¹. The radical trapping test reveals that h⁺ and ^•O₂⁻ take the leading role in the reaction, while the stability test reveals a 98% efficiency after the fourth cycle. As established from various interpretations, the considerably enhanced photocatalytic performance of the heterojunction system can be attributed to the promoted charge carrier separation and transfer of photoexcited carriers, as well as the strong photo-redox ability established. Hence, the S-scheme Pt@BFO/O-CN heterojunction is a good candidate in the treatment of industrial wastewater for the mineralization of organic micropollutants, which pose a grievous threat to the environment. Full article

Photocatalytic processes under visible light have constantly been finding more and more applications in organic synthesis as they allow a wide range of transformations to proceed under mild conditions. The combination of photoredox catalysis with metal complex catalysis gives an opportunity to employ the advantages of these two methodologies. Covalent bonding of photocatalyst and metal complex catalyst using bridging ligands increases the efficiency of the electron and energy transfer between these two parts of the catalyst, leading to more efficient and selective catalytic systems. Up to now, after numerous investigations of the photocatalytic reduction of CO₂ and hydrogen generation, such a strategy was firmly established to substantially increase the catalyst’s activity. This review is aimed at the achievements and perspectives in the field of design and application of heterobinuclear metal complexes as photocatalysts in organic synthesis. Full article

Eosin Y is one of the most popular organic dyes used as a photoredox catalyst and is largely employed in photochemical reactions both as a homogeneous and heterogeneous photocatalyst after immobilization. Immobilization of Eosin Y onto a solid support has many advantages, such as the possibility of recovery and reuse of the photocatalyst and the possibility of its use under flow conditions. In this paper, we report our findings on the immobilization of Eosin Y onto Merrifield resin and its application in the direct photochemical arylation of furan with aryldiazonium salts. The synthesized supported photocatalyst was used in batch reactions under heterogeneous conditions with different aryl diazonium salts, and its recovery and recycle were demonstrated for up to three times. The immobilized photocatalyst was then loaded in a packed-bed reactor and used under continuous flow conditions. The flow reaction allowed the arylated products to be obtained with higher productivity and space-time-yield than the batch in a very short reaction time. Full article

Straightforward and versatile surface modification, functionalization and coating have become a significant topic in material sciences. While physical modification suffers from severe drawbacks, such as insufficient stability, chemical induced grafting processes efficiently modify organic and inorganic materials and surfaces due to covalent linkage. These processes include the “grafting from” method, where polymer chains are directly grown from the surface in terms of a surface-initiated polymerization and the “grafting to” method where a preformed (macro)-molecule is introduced to a preliminary treated surface via a coupling reaction. Both methods require an initiating species that is immobilized at the surface and can be triggered either by heat or light, whereas light induced processes have recently received increasing interest. Therefore, a major challenge is the ongoing search for suitable anchor moieties that provide covalent linkage to the surface and include initiators for surface-initiated polymerization and coupling reactions, respectively. This review containing 205 references provides an overview on photoinitiators which are covalently coupled to different surfaces, and are utilized for subsequent photopolymerizations and photocoupling reactions. An emphasis is placed on the coupling strategies for different surfaces, including oxides, metals, and cellulosic materials, with a focus on surface coupled free radical photoinitiators (type I and type II). Furthermore, the concept of surface initiation mediated by photoiniferters (PIMP) is reviewed. Regarding controlled radical polymerization from surfaces, a large section of the paper reviews surface-tethered co-initiators, ATRP initiators, and RAFT agents. In combination with photoinitiators or photoredox catalysts, these compounds are employed for surface initiated photopolymerizations. Moreover, examples for coupled photoacids and photoacid generators are presented. Another large section of the article reviews photocoupling and photoclick techniques. Here, the focus is set on light sensitive groups, such as organic azides, tetrazoles and diazirines, which have proven useful in biochemistry, composite technology and many other fields. Full article

A Photoinduced dearomative nucleophilic addition to N-Boc indoles mediated by two-molecule organic photoredox catalysts such as phenanthrene and 1,4-dicyanobenzene with UV irradiation furnished 2-substituted indolines in moderate to quantitative yields. Hydroxide, alkoxide, and cyanide ions can be used as a nucleophile to provide 2-hydroxy, 2-alkoxy, and 2-cyanoindolines, respectively. Both electron-rich and -deficient indoles, including tryptophan derivatives, can be employed in the photoreaction to provide various indolines. This method provides transition-metal-free access to 2-subsituted indolines from indoles using organic photoredox catalysts under mild conditions. Full article

The use of organic photoredox catalysts provides new ways to perform metal-free reactions controlled by light. While these reactions are usually performed in organic media, the application of these catalysts at ambient temperatures in aqueous media is of considerable interest. We here compare the activity of two established organic photoredox catalysts, one based on 10-phenylphenothiazine (PTH) and one based on an acridinium dye (ACR), in the light-activated dehalogenation of aromatic halides in pure water. Both PTH and ACR were covalently attached to amphiphilic polymers that are designed to form polymeric nanoparticles with hydrodynamic diameter D_H ranging between 5 and 11 nm in aqueous solution. Due to the hydrophobic side groups that furnish the interior of these nanoparticles after hydrophobic collapse, water-insoluble reagents can gather within the nanoparticles at high local catalyst and substrate concentrations. We evaluated six different amphiphilic polymeric nanoparticles to assess the effect of polymer length, catalyst loading and nature of the catalyst (PTH or ACR) in the dechlorination of a range of aromatic chlorides. In addition, we investigate the selectivity of both catalysts for reducing different types of aryl-halogen bonds present in one molecule, as well as the activity of the catalysts for C-C cross-coupling reactions. We find that all polymer-based catalysts show high activity for the reduction of electron-poor aromatic compounds. For electron-rich compounds, the ACR-based catalyst is more effective than PTH. In the selective dehalogenation reactions, the order of bond stability is C-Cl > C-Br > C-I irrespective of the catalyst applied. All in all, both water-compatible systems show good activity in water, with ACR-based catalysts being slightly more efficient for more resilient substrates. Full article

Directly linked donor and acceptor arenes, such as phenanthrene/naphthalene/biphenyl and 1,3-dicyanobenzene were found to work as photoredox catalysts in the photoreactions of indene, 2,3-dimethyl-2-butene, and 4-methoxyphenylacetic acid. The new stable organic photocatalyst forms an intramolecular exciplex (excited complex) when irradiated in a polar solvent and shows redox catalyst activity, even at low concentrations. To the best of our knowledge, this is the first example of an intramolecular exciplex working as a redox catalyst. Full article

Photocatalyzed polymerization using organic molecules as catalysts has attracted broad interest because of its easy operation in ambient environments and low toxicity compared with metallic catalysts. In this work, we reported that 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DTBT) can act as an efficient photoredox catalyst for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization under green light irradiation. Well-defined (co)polymers can be obtained using this technique without any additional additives like noble metals and electron donors or acceptors. The living characteristics of polymerization were verified by kinetic study and the narrow dispersity (Đ) of the produced polymer. Excellent chain-end fidelity was demonstrated through chain extension as well. In addition, this technique showed great potential for various RAFT agents and monomers including acrylates and acrylamides. Full article