Near-infrared photocatalysis with cyanines: synthesis, applications and perspectives.

Cyanines are organic dyes bearing two aza-heterocycles linked by a polymethine chain. Excited states, fluorescence, redox activity, and energy transfer are interesting properties of cyanines which have been used by chemists. Moreover, they are easily accessible and highly tunable. For all these reasons, cyanines are often selected for applications like fluorescent probes, phototherapy and photovoltaics. However, considering cyanines as photocatalysts is a new field of investigation and has been sparsely reported in the literature. This field of research has been launched on the basis of near-infrared light photocatalysis. With a deeper NIR light penetration, the irradiation is compatible with biological tissues. Due to the longer wavelengths that are involved, the safety of the operator can be guaranteed. In this perspective review, the photophysical/redox properties of cyanines are reported as well as their preparations and applications in modern synthetic approaches. Finally, recent examples of cyanine-based NIR-photocatalysis are discussed including photopolymerization and organic synthesis.

3D-Printed Eosin Y-Based Heterogeneous Photocatalyst for Organic Reactions.

Heterogenization of Eosin Y by 3D-printing and its application in photocatalysis are reported. The approach allows a fine tuning of the photocatalyst morphology and its rapid preparation. Photocatalytic activity was evaluated through model organic reactions involving oxidation, reduction, and photosensitization pathways. The efficiency, recyclability and stability of 3D printed EY is remarkable paving the way to new generation of heterogeneous photocatalysts with a perfect control of their shape and adaptable to any photoreactors.

Second Generation of Near-Infrared Cyanine-Based Photocatalysts for Faster Organic Transformations.

A second generation of cyanine-based near-infrared photocatalysts has been developed to accelerate organic transformations. Cyanines were prepared and fully characterized prior to evaluation of their photocatalytic activities. Catalyst efficiency was determined by using two model oxidation and reduction reactions. For the aza-Henry reaction, cyanines bearing an amino group on the heptamethine chain led to the best results. For trifluoromethylation, the stability of the photocatalyst was found to be the key parameter for efficient and rapid conversion.

Heterogeneous Photoredox Catalysis Based on Silica Mesoporous Material and Eosin Y: Impact of Material Support on Selectivity of Radical Cyclization.

Heterogenization of the photocatalyst appears to be a valuable solution to reach sustainable processes. Rapid and efficient synthesis of supported photocatalyst is still a remaining challenge and the choice of the support material is crucial. The present study aims at preparing a new generation of hybrid inorganic/organic photocatalysts based on silica mesoporous material and Eosin Y. These results highlight the influence of non-covalent interactions between the material support and the reagent impacting the selectivity of the reaction.

Squaraines as near-infrared photocatalysts for organic reactions.

Herein, unprecedented uses of squaraine derivatives as new organic near-infrared photocatalysts are reported. These efficient molecular tools are able to promote oxidation and reduction for organic transformations through photocatalytic conditions. A mechanistic investigation is performed to distinguish between competitive Single Electron Transfer and Energy Transfer pathways.

Cyanine-based near infra-red organic photoredox catalysis.

Direct metal-free near infra-red photoredox catalysis is applied to organic oxidation, photosensitization and reduction, involving cyanines as photocatalysts. This photocatalyst is competitive with conventional reactions catalyzed under visible light. Kinetic and quenching experiments are also reported. Interestingly, these systems are compatible with water media, opening perspective for various applications.

Characterization in aqueous medium of an FMN semiquinone radical stabilized by the enzyme-like microenvironment of a modified polyethyleneimine.

The elusive flavin semiquinone intermediate found in flavoproteins such as cryptochromes has been obtained in aqueous solution by single electron reduction of the natural FMN cofactor using sodium ascorbate. This species was formed in the local hydrophobic microenvironment of a modified polyethyleneimine and characterized by UV-Visible, fluorescence and EPR spectroscopies.

Aerobic Baeyer-Villiger Oxidation Catalyzed by a Flavin-Containing Enzyme Mimic in Water.

Direct incorporation of molecular oxygen into small organic molecules has attracted much attention for the development of new environmentally friendly oxidation processes. In line with this approach, bioinspired systems mimicking enzyme activities are of particular interest since they may perform catalysis in aqueous media. Demonstrated herein is the incorporation of a natural flavin cofactor (FMN) into the specific microenvironment of a water-soluble polymer which allows the efficient reduction of the FMN by NADH in aqueous solution. Once reduced, this artificial flavoenzyme can then activate molecular dioxygen under aerobic conditions and result in the Baeyer-Villiger reaction at room temperature in water.

Photoredox Catalysis for the Generation of Carbon Centered Radicals.

Radical chemistry has witnessed over the last decades important advances that have positioned it as a methodology of choice in synthetic chemistry. A number of great attributes such as specific reactivities, the knowledge of the kinetics of most elementary processes, the functional group tolerance, and the possibility to operate cascade sequences are clearly responsible for this craze. Nevertheless, at the end of the last century, radical chemistry appeared plagued by several hurdles to overcome such as the use of environmentally problematic mediators or the impossibility of scale up. While the concept of photocatalysis was firmly established in the coordination chemistry community, its diffusion in organic synthetic chemistry remained sporadic for decades until the end of the 2000s with the breakthrough merging of organocatalysis and photocatalysis by the MacMillan group and contemporary reports by the groups of Yoon and Stephenson. Since then, photoredox catalysis has enjoyed particularly active and intense developments. It is now the topic of a still increasing number of publications featuring various applications from asymmetric synthesis, total synthesis of natural products, and polymerization to process (flow) chemistry. In this Account, we survey our own efforts in this domain, focusing on the elaboration of new photocatalytic pathways that could lead to the efficient generation of C-centered functionalized alkyl and aryl radicals. Both reductive and oxidative manifolds are accessible through photoredox catalysis, which has guided us along these lines in our projects. Thus, we studied the photocatalytic reduction of onium salts such as sulfoniums and iodoniums for the production of the elusive aryl radical intermediates. Progressing to more relevant chemistry for synthesis, we examined the cleavage of C-O and the C-Br bonds for the generation of alkyl C-centered radicals. Activated epoxides could serve as valuable substrates of a photocatalyzed variant of the Nugent-RajanBabu-Gansäuer homolytic cleavage of epoxides. Using imidazole based carbamates, we could also devise the first photocatalyzed Barton-McCombie deoxygenation reaction. Finally, bromophenylacetate can be reduced using the [Au2(µ-dppm)2]Cl2 photocatalyst under UVA or visible-light. This was used for the initiation of the controlled atom transfer radical polymerization of methacrylates and acrylates in solution or laminate. Our next endeavors concerned the photocatalyzed oxidation of stabilized carbanions such as enolates of 1,3-dicarbonyl substrates, trifluoroborates, and more extensively bis-catecholato silicates. Because of their low oxidation potentials, the later have proved to be exquisite sources of radical entities, which can be engaged in diverse intermolecular reactions such as vinylation, alkynylation, and conjugate additions. The bis-catecholato silicates were also shown to behave as excellent partners of dual photoredox-nickel catalysis leading in an expeditious manner to libraries of cross coupling products.

Fluorescent Brighteners as Visible LED-Light Sensitive Photoinitiators for Free Radical Photopolymerizations.

The photochemical and electrochemical investigations of commercially available, safe, and cheap fluorescent brighteners, namely, triazinylstilbene (commercial name: fluorescent brightener 28) and 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene, as well as their original use as photoinitiators of polymerization upon light emitting diode (LED) irradiation are reported. Remarkably, their excellent near-UV-visible absorption properties combined with outstanding fluorescent properties allow them to act as high-performance photoinitiators when used in combination with diaryliodonium salt. These two-component photoinitiating systems can be employed for free radical polymerizations of acrylate. In addition, this brightener-initiated photopolymerization is able to overcome oxygen inhibition even upon irradiation with low LED light intensity. The underlying photochemical mechanisms are investigated by electron-spin resonance-spin trapping, fluorescence, cyclic voltammetry, and steady-state photolysis techniques.

Metal-free arylation of pyrimidines through a photochemical process.

Pyrimidinyl and pyrazinyl radicals were generated under moderate energetic irradiation conditions (UVA), and proved to be prompt to undergo C-C bond formation processes. Hetero-biaryl derivatives were obtained in good to high yields with highly interesting functional group selectivities. Bis hetero-biaryls were also easily accessible leading to original compounds, ready for further transformations. Experiments supporting radical processes have been reported.

Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds.

This works introduces hypervalent bis-catecholato silicon compounds as versatile sources of alkyl radicals upon visible-light photocatalysis. Using Ir[(dF(CF3)ppy)2(bpy)](PF6) (dF(CF3)ppy = 2-(2,4-difluorophenyl)-5-trifluoromethylpyridine, bpy = bipyridine) as catalytic photooxidant, a series of alkyl radicals, including highly reactive primary ones can be generated and engaged in various intermolecular homolytic reactions. Based on cyclic voltammetry, Stern-Volmer studies, and supported by calculations, a mechanism involving a single-electron transfer from the silicate to the photoactivated iridium complex has been proposed. This oxidative photocatalyzed process can be efficiently merged with nickel-catalyzed Csp2-Csp3 cross-coupling reactions.

Versatile access to Martin's spirosilanes and their hypervalent derivatives.

A new route to Martin's spirosilanes has been devised. The original synthesis does not allow diversely substituted spirosilane derivatives to be synthesized, and thus their corresponding silicates. In this report, Martin's spirosilanes bearing alkyl, aryl, halogen, alkoxy, and trifluoromethyl substituents on the aryl ring have been prepared through a versatile four-step route. Addition of fluoride onto these Lewis acids as a prototypical reaction with a nucleophile yielded a library of stable fluorosilicates. Both sets of compounds have been characterized by X-ray crystallography.

N-heterocyclic carbene-initiated hydrosilylation of styryl alcohols with dihydrosilanes: a mechanistic investigation.

Investigation of the mechanism of the NHC-initiated hydrosilylation of styryl alcohols in the presence of a dihydrosilane suggests a general base catalysis mechanism and not the activation of the dihydrosilane by the NHC.

Spirosilane derivatives as fluoride sensors.

Spirosilane derivatives have been investigated as fluoride sensors. The reactions between these compounds and different fluoride sources, which resulted in structural alterations, have been monitored and quantified by UV and fluorescence spectroscopy. The high selectivity of these probes for fluoride ions has been demonstrated in either organic or aqueous media.

Homolytic reduction of onium salts.

Onium salts have proved to be efficient sources of carbon-centered radicals. They can undergo homolytic reduction by single electron transfer (SET) and participate in subsequent synthetic transformations. This review aims to provide an overview on the behavior of onium salts including diazonium, sulfonium, selenonium, telluronium, phosphonium and iodonium cations toward various reductive methods such as radiolysis, electrolysis, photolysis or the use of SET reagents. Mechanistic and synthetic aspects are presented. Applications in polymers and materials science are not covered.

Combination of gold catalysis and Selectfluor for the synthesis of fluorinated nitrogen heterocycles.

We herein report the synthesis of 3-fluoro-2-methylene-pyrrolidine (3a) and -piperidine (3b) from 1,5- and 1,6-aminoalkynes, respectively, using a combination of a gold-catalyzed hydroamination reaction followed by electrophilic trapping of an intermediate cyclic enamine by Selectfluor. Careful attention was paid to the elucidation of the mechanism and Selectfluor was suggested to play the double role of promoting the oxidation of gold(I) to a gold(III) active species and also the electrophilic fluorination of the enamine intermediates.