Visible photons as ideal reagents for the activation of coloured organic compounds.

In recent decades, the traceless nature of visible photons has been exploited for the development of efficient synthetic strategies for the photoconversion of colourless compounds, namely, photocatalysis, chromophore activation, and the formation of an electron donor/acceptor (EDA) complex. However, the use of photoreactive coloured organic compounds is the optimal strategy to boost visible photons as ideal reagents in synthetic protocols. In view of such premises, the present review aims to provide its readership with a collection of recent photochemical strategies facilitated via direct light absorption by coloured molecules. The protocols have been classified and presented according to the nature of the intermediate/excited state achieved during the transformation.

Visible-Light-Mediated Divergent and Regioselective Vicinal Difunctionalization of Styrenes with Arylazo Sulfones.

Activated by visible light, arylazo sulfones can serve as multifaceted reactants and are employed in diazenylation, sulfonylation, and arylation reactions under (photo)catalyst-free conditions. Such versatile reactivity enabled us to develop an operationally simple, regioselective, and tunable difunctionalization of styrenes with arylazo sulfones to produce α-sulfonyl arylhydrazones and 1,2-alkoxyarylated products in moderate to excellent yields. Furthermore, such difunctionalized products have been exploited as key building blocks for the synthesis of various heterocycles.

Friedel-Crafts arylation of aldehydes with indoles utilizing arylazo sulfones as the photoacid generator.

A versatile, inexpensive and sustainable protocol for the preparation of valuable bis-indolyl methanes via visible light-mediated, metal-free Friedel-Crafts arylation has been developed. The procedure, that exploits the peculiar behavior of arylazo sulfones as non-ionic photoacid generators (PAGs), was applied to the conversion of a variety of aliphatic and aromatic aldehydes into diarylmethanes in good to highly satisfactory yields, employing a low-catalyst loading (0.5 mol%) and irradiation at 456 nm.

A General Metal-Free Protocol for the Visible-Light-Driven Protection of Carbonyls.

The protection of a carbonyl is a standard procedure to mask the reactivity of this group towards nucleophiles and reductants. The present work pointed out the potentialities of arylazo sulfones as non-ionic photoacid generators (PAGs) to promote the efficient conversion of aldehydes and ketones into acetals, ketals, and 1,3-oxazolidines upon visible-light irradiation. This approach employed mild conditions and exhibited an easy scalability and a broad scope (80 examples included).

Arylazo Sulfones as Nonionic Visible-Light Photoacid Generators.

The selective visible-light-driven generation of a weak acid (sulfinic acid, in nitrogen-purged solutions) or a strong acid (sulfonic acid, in oxygen-purged solutions) by using shelf-stable arylazo sulfones was developed. These sulfones were then used for the green, smooth, and efficient photochemical catalytic protection of several (substituted) alcohols (and phenols) as tetrahydropyranyl ethers or acetals.

Visible Light-Driven, Gold(I)-Catalyzed Preparation of Symmetrical (Hetero)biaryls by Homocoupling of Arylazo Sulfones.

The preparation of symmetrical (hetero)biaryls via arylazo sulfones has been successfully carried out upon visible light irradiation in the presence of PPh3AuCl as the catalyst. The present protocol led to the efficient synthesis of a wide range of target compounds in an organic-aqueous solvent under photocatalyst-free conditions.

Diradicals Photogeneration from Chloroaryl-Substituted Carboxylic Acids.

With the aim of generating new, thermally inaccessible diradicals, potentially able to induce a double-strand DNA cleavage, the photochemistry of a set of chloroaryl-substituted carboxylic acids in polar media was investigated. The photoheterolytic cleavage of the Ar-Cl bond occurred in each case to form the corresponding triplet phenyl cations. Under basic conditions, the photorelease of the chloride anion was accompanied by an intramolecular electron-transfer from the carboxylate group to the aromatic radical cationic site to give a diradical species. This latter intermediate could then undergo CO2 loss in a structure-dependent fashion, according to the stability of the resulting diradical, or abstract a hydrogen atom from the medium. In aqueous environment at physiological pH (pH=7.3), both a phenyl cation and a diradical chemistry was observed. The mechanistic scenario and the role of the various intermediates (aryl cations and diradicals) involved in the process was supported by computational analysis.

Aryl-Cl vs heteroatom-Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals.

The photochemistry of aryl chlorides having a X-SiMe3 group (X = O, NR, S, SiMe2) tethered to the aromatic ring has been investigated in detail, with the aim to generate valuable Ï­,π-heterodiradicals. Two competitive pathways arising from the excited triplet state of the aromatics have been observed, namely heterolysis of the aryl-chlorine bond and homolysis of the X-silicon bond. The former path is found in chlorinated phenols and anilines, whereas the latter is exclusive in the case of silylated thiophenols and aryl silanes. A combined experimental/computational approach was pursued to explain such a photochemical behavior.Graphical abstract.