Unlocking Photocatalytic Activity of Acridinium Salts by Anion-Binding Co-Catalysis.

The in situ generation of active photoredox organic catalysts upon anion-binding co-catalysis by making use of the ionic nature of common photosensitizers is reported. Hence, the merge of anion-binding and photocatalysis permitted the modulation of the photocatalytic activity of simple acridinium halide salts, building an effective anion-binding - photoredox ion pair complex able to promote a variety of visible light driven transformations, such as anti-Markovnikov addition to olefins, Diels-Alder and the desilylative C-C bond forming reactions. Anion-binding studies, together with steady-state and time-resolved spectroscopy analysis, supported the postulated ion pair formation between the thiourea hydrogen-bond donor organocatalyst and the acridinium salt, which proved essential for unlocking the photocatalytic activity of the photosensitizer.

A new green-to-blue upconversion system with efficient photoredox catalytic properties.

The design and development of new triplet-triplet annihilation upconversion (TTA-UC) systems combining triplet sensitizers with acceptor compounds have attracted considerable interest. In this vein, sensitizers made from purely organic dyes rather than transition-metal complexes appear to be more convenient from an environmental point of view. BODIPYs are a very well-known class of dyes with applications in a widespread range of scientific areas. Owing to the versatility of BODIPYs, we present herein a new asymmetric BODIPY with excellent photophysical properties to be used as an appropriate sensitizer in a bimolecular TTA-UC system. Detailed spectroscopic measurements demonstrated the ability of this new design to sensitize TTA-UC by combination with a suitable acceptor such as 2,5,8,11-tetra-tert-butylperylene (TBPe), allowing a successful conversion of green to blue light. The singlet-excited TBPe so obtained is capable of activating aryl chlorides reductively which initiated the functionalization of N-methylpyrrole (Meerwein-type arylation) and formation of both substituted triarylethylenes (Mizoroki-Heck reaction) and heteroarene phosphonates (photo-Arbuzov reaction). Product yields reveal that our TTA-UC system behaved as a highly efficient photocatalytic entity.

Effective Formation of New C(sp2 )-S Bonds via Photoactivation of Alkylamine-based Electron Donor-Acceptor Complexes.

A novel visible light promoted formation of CAryl- S bonds through electron donor-acceptor (EDA) complexes of alkylamines with 5- and 6-membered (hetero)arene halides is presented. This represents the first EDA-based thiolation method not relying on π-π or a thiolate-anion-π interactions and provides a facile access to heteroarene radicals, which can be suitably trapped by disulfide derivatives to form the corresponding versatile arylsulfides. Mechanistic investigations on the aspects of the whole process were conducted by spectroscopic measurements, demonstrating the hypothesized EDA complex formation. Moreover, the strength of this method has been proven by a gram-scale synthesis of thiolated products and the late-stage derivatization of an anticoagulant drug.

Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis.

A new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes with excellent yields using dichromatic photoredox catalysis in a gel-based nanoreactor is described here. The procedure involves visible aerobic irradiation (cold white LEDs) of a mixture containing the heteroarene halide, trisubstituted phospite, N,N-diisopropylethylamine (DIPEA) as sacrificial agent, and catalytic amounts of 9,10-dicyanoanthracene (DCA) in the presence of an adequate gelator, which permits a faster process than at the homogeneous phase. The methodology, which operates by a consecutive photoinduced electron transfer (ConPET) mechanism, has been successfully applied to the straightforward and clean synthesis of a number of different heteroarene (furan, thiophene, selenophene, pyrrole, oxazole, or thioxazole) phosphonates, extending to the late-stage phosphonylation of the anticoagulant rivaroxaban. Strategically, employment of cold white light is critical since it provides both selective wavelengths for exciting first DCA (blue region) and subsequently its corresponding radical anion DCA•- (green region). The resultant strongly reducing excited agent DCA•-* is capable of even activate five-membered heteroarene halides (Br, Cl) with high reduction potentials (∼-2.7 V) to effect the C(sp2)-P bond formation. Spectroscopic and thermodynamic studies have supported the proposed reaction mechanism. Interestingly, the rate of product formation has been clearly enhanced in gel media because reactants can be presumably localized not only in the solvent pools but also through to the fibers of the viscoelastic gel network. This has been confirmed by field-emission scanning electron microscopy images where a marked densification of the network has been observed, modifying its fibrillary morphology. Finally, rheological measurements have shown the resistance of the gel network to the incorporation of the reactants and the formation of the desired products.

Aerobic Visible-Light-Driven Borylation of Heteroarenes in a Gel Nanoreactor.

Heteroarene boronate esters constitute valuable intermediates in modern organic synthesis. As building blocks, they can be further applied to the synthesis of new materials, since they can be easily transformed into any other functional group. Efforts toward novel and efficient strategies for their preparation are clearly desirable. Here, we have achieved the borylation of commercially available heteroarene halides under very mild conditions in an easy-to-use gel nanoreactor. Its use of visible light as the energy source at room temperature in photocatalyst-free and aerobic conditions makes this protocol very attractive. The gel network provides an adequate stabilizing microenvironment to support wide substrate scope, including furan, thiophene, selenophene, and pyrrole boronate esters.

Rapid Access to Borylated Thiophenes Enabled by Visible Light.

Boron-containing thiophenes are important entities in organic/medicinal chemistry as well as in material science. In this Letter, a novel, straightforward, and fast procedure for their production employing visible light as an energy source at room temperature and ambient pressure is reported. All substrates are commercially available, and the process does not require the use of any external photocatalyst.