Unveiling the Untapped Potential of Bertagnini's Salts in Microwave-Assisted Synthesis of Quinazolinones.

Microwave-assisted organic synthesis (MAOS) has emerged as a transformative technique in organic chemistry, significantly enhancing the speed, efficiency, and selectivity of chemical reactions. In our research, we have employed microwave irradiation to expedite the synthesis of quinazolinones, using water as an eco-friendly solvent and thereby adhering to the principles of green chemistry. Notably, the purification of the product was achieved without the need for column chromatography, thus streamlining the process. A key innovation in our approach is using aldehyde bisulfite adducts (Bertagnini's salts) as solid surrogates of aldehydes. Bertagnini's salts offer several advantages over free aldehydes, including enhanced stability, easier purification, and improved reactivity. Green metrics and Eco-Scale score calculations confirmed the sustainability of this approach, indicating a reduction in waste generation and enhanced sustainability outcomes. This methodology facilitates the synthesis of a diverse array of compounds, offering substantial contributions to the field, with potential for widespread applications in pharmaceutical research and beyond.

Electronic Effects in a Green Protocol for (Hetero)Aryl-S Coupling.

Aryl and heteroaryl iodides have been efficiently converted into the corresponding thioacetates in cyclopentyl methyl ether (CPME), a green solvent, under Cu catalysis. The chemoselectivity of the reaction is mainly controlled by electronic factors, enabling the conversion of both electron-rich and electron-deficient substrates into the corresponding thioacetates in good to excellent yields. The products can be easily deprotected to the corresponding thiolates to carry out additional synthetic transformations in situ. Surprisingly, despite CPME's relatively low dielectric constant, the reaction rate significantly increased when conducted under microwave irradiation conditions. This synthetic methodology exhibits a remarkable tolerance to functional groups, mild reaction conditions, and a wide substrate scope, utilizing a safe and inexpensive CuI pre-catalyst in the green solvent CPME. A non-aqueous workup allowing for the complete recovery of both catalyst and solvent makes this approach an environmentally sustainable protocol for C(sp2) sulfur functionalization. Additionally, the reaction shows selective cross-coupling with iodides in competition with chlorides and bromides, allowing its use in multistep syntheses. To demonstrate the potential of this methodology, it was applied to the high-yield synthesis of a photochromic dithienylethene, where a selective synthesis had not been reported before.

Visible Light-Promoted Oxidative Cross-Coupling of Alcohols to Esters.

Ester is one of the most significant functional groups in organic chemistry and is enclosed in several valued molecules. Usually, esters are prepared through the acid-catalyzed esterification reaction of carboxylic acids with alcohols, transesterification of esters with alcohols, or via activation of carboxylic acids followed by the addition of alcohols. However, these procedures typically imply the excess use of reactants and harsh reaction conditions. Visible light-mediated photoreactions have been disclosed to display a safe, sustainable, and accessible alternative to traditional methods, and to lead new reactivity modes in organic procedures. In this context, we propose a transition metal-based and organic-based photocatalyst-free synthesis of esters from alcohols induced by visible light. The methodology can be carried out using sunlight or artificial visible light as a solar simulator or a blue LED source.

N-Alkylation of aromatic amines with alcohols by using a commercially available Ru complex under mild conditions.

An N-alkylation procedure has been developed under very mild conditions using a known commercially available Ru-based catalyst. As a result, a wide range of aromatic primary amines has been selectively alkylated with several primary alcohols, yielding the corresponding secondary amines in high yields. The methodology also enables the methylation of anilines in refluxing methanol and the preparation of a set of heterocycles in a straightforward way.

Mechanochemistry Frees Thiourea Dioxide (TDO) from the 'Veils' of Solvent, Exposing All Its Reactivity.

The synthesis of nitrogen-based heterocycles has always been considered essential in developing pharmaceuticals in medicine and agriculture. This explains why various synthetic approaches have been proposed in recent decades. However performing as methods, they often imply harsh conditions or the employment of toxic solvents and dangerous reagents. Mechanochemistry is undoubtedly one of the most promising technologies currently used for reducing any possible environmental impact, addressing the worldwide interest in counteracting environmental pollution. Following this line, we propose a new mechanochemical protocol for synthesizing various heterocyclic classes by exploiting thiourea dioxide (TDO)'s reducing proprieties and electrophilic nature. Simultaneously exploiting the low cost of a component of the textile industry such as TDO and all the advantages brought by a green technique such as mechanochemistry, we plot a route towards a more sustainable and eco-friendly methodology for preparing heterocyclic moieties.

Mechanochemistry: New Tools to Navigate the Uncharted Territory of "Impossible" Reactions.

Mechanochemical transformations have made chemists enter unknown territories, forcing a different chemistry perspective. While questioning or revisiting familiar concepts belonging to solution chemistry, mechanochemistry has broken new ground, especially in the panorama of organic synthesis. Not only does it foster new "thinking outside the box", but it also has opened new reaction paths, allowing to overcome the weaknesses of traditional chemistry exactly where the use of well-established solution-based methodologies rules out progress. In this Review, the reader is introduced to an intriguing research subject not yet fully explored and waiting for improved understanding. Indeed, the study is mainly focused on organic transformations that, although impossible in solution, become possible under mechanochemical processing conditions, simultaneously entailing innovation and expanding the chemical space.

Aquivion perfluorosulfonic superacid as an effective catalyst for selective epoxidation of vegetable oils.

The acid-promoted epoxidation of vegetable oils was studied using a variety of acidic ion exchange resins as heterogeneous acid catalysts. Quantitative and selective epoxidation of a series of vegetable oils with different composition of saturated, mono-, di- and tri-unsaturated fatty acids was obtained upon identification of the more efficient catalyst and experimental conditions. Furthermore, optimized reaction conditions were successfully applied to the epoxidation of a waste cooking oil, thus extending our procedure to the valorization of a biowaste, an area of increasing importance within a more sustainable society. The use of quantitative 1HNMR besides making accurate evaluation of the amounts of reagents to be employed and of the selectivity, allowed facile and rapid quantification of mono-, di- and tri-epoxides, thus providing an indirect indication on the fatty acid composition of the vegetable oils, even in the presence of very low quantities of linolenic acid.

Appealing Renewable Materials in Green Chemistry.

In just a few years, chemists have significantly changed their approach to the synthesis of organic molecules in the laboratory and industry. Researchers are encouraged to approach "greener" reagents, solvents, and methodologies, to go hand in hand with the world's environmental matter, such as water, soil, and air pollution. The employment of plant and animal derivates that are commonly regarded as "waste material" has paved the way for the development of new green strategies. In this review, the most important innovations in this field have been highlighted, paying due attention to those materials that have played a crucial role in organic reactions: wool, silk, and feather. Moreover, we decided to focus on the other most important supports and catalysts in green syntheses, such as proteins and their derivates. Different materials have shown prominent activity in the adsorption of metals and organic dyes, which has constituted a relevant scope in the last two decades. We intend to furnish a complete screening of the application given to these materials and contribute to their potential future utilization.

Comparative Evaluation of Graphene Nanostructures in GERS Platforms for Pesticide Detection.

Graphene-enhanced Raman scattering (GERS) produces enhancement of the Raman signal, which is based on chemical rather than electromagnetic mechanism such as in the surface-enhanced Raman scattering. Graphene oxide, amino- and guanidine-functionalized graphene oxide, exfoliated graphene, and commercial graphene nanoplatelets have been used to investigate the GERS response with the change of graphene properties. Different graphene nanostructures have been embedded into organic-inorganic microporous films to build a platform for the fast and sensitive detection of pesticides in water. The graphene nanostructures vary in the number of layers, lateral size, degree of oxidation, and surface functionalization. The GERS performances of the graphene nanostructures cast on silicon substrates and embedded in the nanocomposite films have been comparatively evaluated. After casting a few droplets of the pesticide aqueous solution on the graphene nanostructures, the Raman band enhancements of the analytes have been measured. In the nanocomposite films, the characteristic Raman bands originating from pesticides such as paraoxon, parathion, and glyphosate could be traced at concentrations below 10-7, 10-5, and 10-4 M, respectively. The results show that the surface functionalization reduces the GERS effect because it increases the ratio between the sp3 carbon and sp2 carbon. On the other hand, the comparison among different types of graphenes shows that the monolayers are more efficient than the few-layer nanostructures in enhancing the Raman signal.

Visible-Light Photoredox-Catalyzed Amidation of Benzylic Alcohols.

A new photocatalyzed route to amides from alcohols and amines mediated by visible light is presented. The reaction is carried out in ethyl acetate as a solvent. Ethyl acetate can be defined a green and bio-based solvent. The starting materials such as the energy source are easily available, stable, and inexpensive. The reaction has shown to be general and high yielding.

Metal-free mechanochemical oxidations in Ertalyte® jars.

Aimed at eliminating or at least significantly reducing the use of solvents, sodium hypochlorite pentahydrate crystals (NaOCl·5H2O) in the presence of a catalytic amount of a nitrosyl radical (TEMPO or AZADO) have been successfully used to induce mechanochemical oxidative processes on several structurally different primary and secondary alcohols. The proposed redox process is safe, inexpensive and performing effectively, especially on the macroscale. Herein, an Ertalyte® jar has been successfully used, for the first time, in a mechanochemical process.

Mechanically induced oxidation of alcohols to aldehydes and ketones in ambient air: Revisiting TEMPO-assisted oxidations.

The present work addresses the development of an eco-friendly and cost-efficient protocol for the oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones by mechanical processing under air. Ball milling was shown to promote the quantitative conversion of a broad set of alcohols into carbonyl compounds with no trace of an over-oxidation to carboxylic acids. The mechanochemical reaction exhibited higher yields and rates than the classical, homogeneous, TEMPO-based oxidation.

Synthesis of Nitric Oxide Donors Derived from Piloty's Acid and Study of Their Effects on Dopamine Secretion from PC12 Cells.

This study investigated the mechanisms and kinetics of nitric oxide (NO) generation by derivatives of Piloty's acid (NO-donors) under physiological conditions. In order to qualitatively and quantitatively measure NO release, electron paramagnetic resonance (EPR) was carried out with NO spin trapping. In addition, voltammetric techniques, including cyclic voltammetry and constant potential amperometry, were used to confirm NO release from Piloty's acid and its derivatives. The resulting data showed that Piloty's acid derivatives are able to release NO under physiological conditions. In particular, electron-withdrawing substituents favoured NO generation, while electron-donor groups reduced NO generation. In vitro microdialysis, performed on PC12 cell cultures, was used to evaluate the dynamical secretion of dopamine induced by the Piloty's acid derivatives. Although all the studied molecules were able to induce DA secretion from PC12, only those with a slow release of NO have not determined an autoxidation of DA itself. These results confirm that the time-course of NO-donors decomposition and the amount of NO released play a key role in dopamine secretion and auto-oxidation. This information could drive the synthesis or the selection of compounds to use as potential drugs for the therapy of Parkinson's disease (PD).

Metal-Free Direct Oxidation of Aldehydes to Esters Using TCCA.

Aromatic and aliphatic aldehydes are simply converted into esters by an efficient oxidative esterification carried out under mild conditions. The aldehydes are converted in situ into their corresponding acyl chlorides, which are then reacted with primary and secondary aliphatic, benzylic, allylic, and propargylic alcohols and phenols. A variety of esters are obtained in high yields.

Synthesis of α,ß-unsaturated aldehydes based on a one-pot phase-switch dehydrogenative cross-coupling of primary alcohols.

An efficient one-pot ruthenium-catalyzed hydrogen-transfer strategy for a direct access to α,ß-unsaturated aldehydes has been developed. The employment of enolates prepared in situ from alcohols avoided handling unstable aldehydes and provided a very appealing route to different cinnamaldehydes substituted in position 2. A silica-grafted amine was used as phase-switch tag leading to a selective one-pot process in favor of cross-dehydrogenative coupling products.

A two-step tandem reaction to prepare hydroxamic acids directly from alcohols.

The first synthesis of hydroxamic acids from alcohols has been developed. Both benzylic and aliphatic alcohols can be tolerated and applied in this reaction. The methodology is economical, environmentally benign and high yielding.

A copper-catalysed amidation of aldehydes via N-hydroxysuccinimide ester formation.

A copper-catalysed oxidative amidation of aldehydes via N-hydroxysuccinimide ester formation is reported. The methodology employed to prepare amides directly from aldehydes has a very wide scope, is high yielding, and does not need dry conditions. This cross-coupling reaction appears to be simple and makes use of cheap, abundant and easily available reagents.

Iron-catalysed oxidative amidation of alcohols with amines.

A new iron-catalysed oxidative amidation of differently substituted benzylic alcohols with mono- and di-substituted amines was developed.

From alcohols to indoles: a tandem Ru catalyzed hydrogen-transfer Fischer indole synthesis.

In a new version of the Fischer indole synthesis, primary and secondary alcohols have been catalytically oxidized in the presence of phenylhydrazines and protic or Lewis acids to give the corresponding indoles. The overall reaction can be accomplished in one step, and the use of alcohols instead of aldehyes or ketones as starting materials has several advantages in terms of a large selection of reagents, easy handling, and safety of the process.

One-pot synthesis of amides from aldehydes and amines via C-H bond activation.

A one-pot synthesis of amides from aldheydes with N-chloroamines, prepared in situ from amines, has been developed. Both aliphatic and aromatic aldehydes and many types of mono- and disubstituted amines are tolerant in this transformation. This cross-coupling reaction appears simple and convenient, has a wide substrate scope and makes use of cheap, abundant, and easily available reagents.