Emission of light by matter can occur through a variety of mechanisms. When it results from an electronically excited state of a species produced by a chemical reaction, it is called chemiluminescence (CL). The phenomenon can take place both in natural and artificial chemical systems and it has been utilized in a variety of applications. In this review, we aim to revisit some of the latest CL applications based on direct and indirect production modes. The characteristics of the chemical reactions and the underpinning CL mechanisms are thoroughly discussed in view of studies from the very recent bibliography. Different methodologies aiming at higher CL efficiencies are summarized and presented in detail, including CL type and scaffolds used in each study. The CL role in the development of efficient therapeutic platforms is also discussed in relation to the Reactive Oxygen Species (ROS) and singlet oxygen (¹O₂) produced, as final products. Moreover, recent research results from our team are included regarding the behavior of commonly used photosensitizers upon chemical activation under CL conditions. The CL prospects in imaging, biomimetic organic and radical chemistry, and therapeutics are critically presented in respect to the persisting challenges and limitations of the existing strategies to date.

We investigated the catalytic efficacy of supported gold nanoparticles (AuNPs) towards the selective reaction between o-phenylenediamine and aldehydes that yields 2-substituted benzimidazoles. Among several supported gold nanoparticle platforms, the Au/TiO₂ provides a series of 2-aryl and 2-alkyl substituted benzimidazoles at ambient conditions, in the absence of additives and in high yields, using the mixture CHCl₃:MeOH in ratio 3:1 as the reaction solvent. Among the AuNPs catalysts used herein, the Au/TiO₂ containing small-size nanoparticles is found to be the most active towards the present catalytic methodology. The Au/TiO₂ can be recovered and reused at least five times without a significant loss of its catalytic efficacy. The present catalytic synthetic protocol applies to a broad substrate scope and represents an efficient method for the formation of a C–N bond under mild reaction conditions. Notably, this catalytic methodology provides the regio-isomer of the anthelmintic drug, Thiabendazole, in a lab-scale showing its applicability in the efficient synthesis of such N-heterocyclic molecules at industrial levels.

The bifunctional catalytic efficacy of alumina-supported gold nanoparticles (Au/Al₂O₃) was investigated for the synthesis of a series of 2-amino-3-aryl-imidazopyridines through the chemoselective reduction of the corresponding 2-nitro-3-aryl-imidazo[1,2-a]pyridines in high isolated yields. This highly efficient protocol was initially applied for the synthesis of 2-nitro-3-aryl imidazo[1,2-a]pyridines via the reaction between 2-aminopyridine and nitroalkenes catalyzed by the present catalytic system Au/Al₂O₃. Moreover, the heterogeneous surface γ-Al₂O₃ was also found to catalyze this pathway in a comparable manner. However, only Au/Al₂O₃ was further proved as the appropriate catalytic system for the selective transfer hydrogenation of the synthesized 2-nitro imidazopyridine derivatives into the corresponding 2-amino-3-aryl imidazo[1,2-a]pyridines using NaBH₄ as a hydrogen-donor molecule. In addition, the one-pot two-step reaction between nitroalkenes and aminopyridines in the presence of Au/Al₂O₃–NaBH₄ provided directly the fast and facile synthesis of 2-amino-3-aryl imidazopyridines, highlighting a useful synthetic application of the catalytic protocol.

The synthesis of 3,4-dihydroquinoxalin-2-ones via the selective reduction of aromatic, multifunctional nitro precursors catalyzed by supported gold nanoparticles is reported. The reaction proceeds through the in situ formation of the corresponding amines under heterogeneous transfer hydrogenation of the initial nitro compounds catalyzed by the commercially available Au/TiO₂-Et₃SiH catalytic system, followed by an intramolecular C-N transamidation upon treatment with silica acting as a mild acid. Under the present conditions, the Au/TiO₂-TMDS system was also found to catalyze efficiently the present selective reduction process. Both transfer hydrogenation processes showed very good functional-group tolerance and were successfully applied to access more structurally demanding products bearing other reducible moieties such as chloro, aldehyde or methyl ketone. An easily scalable (up to 1 mmol), low catalyst loading (0.6 mol%) synthetic protocol was realized, providing access to this important scaffold. Under these mild catalytic conditions, the desired products were isolated in good to high yields and with a TON of 130. A library analysis was also performed to demonstrate the usefulness of our synthetic strategy and the physicochemical profile of the derivatives.

In this study, commercially available molybdenum carbide (Mo₂C) was used, in the presence of H₂O₂, as an efficient pre-catalyst for the selective C-H allylic oxygenation of several unsaturated molecules into the corresponding allylic alcohols. Under these basic conditions, an air-stable, molybdenum-based polyoxometalate cluster (Mo-POM) was formed in situ, leading to the generation of singlet oxygen (¹O₂), which is responsible for the oxygenation reactions. X-ray diffraction, SEM/EDX and HRMS analyses support the formation mainly of the Mo₆O₁₉²⁻ cluster. Following the proposed procedure, a series of cycloalkenes, styrenes, terpenoids and methyl oleate were successfully transformed into hydroperoxides. After subsequent reduction, the corresponding allylic alcohols were produced with good yields and in lab-scale quantities. A mechanistic study excluded a hydrogen atom transfer pathway and supported the twix-selective oxygenation of cycloalkenes on the more sterically hindered side via the ¹O₂ generation.

A new perspective on the reactivity of hydroxyquinones was revealed as an acetal derivative of lawsone was synthesized, isolated, and used in tandem Knoevenagel/hetero-Diels–Alder reactions catalyzed by S-proline. The intermediate alkylidene-1,3-diones that were formed in situ reacted with electron rich alkenes to predominantly afford pyrano-1,2-naphthoquinone (β-lapachone) derivatives along with the isomeric pyrano-1,4-naphthoquinone (α-lapachone) derivatives in high to excellent total yields. Interestingly, the highly reactive arylidene-1,3-dione derivatives were found to be stable and isolable. DFT calculations suggest that these hetero-Diels–Alder reactions have a high polar character, taking place through a two-stage one-step mechanism. An analysis of the conceptual DFT indices allows explaining the remarkable site-selectivity observed.