Metal-Free Photoredox Catalyzed Sulfonylation of Phenylhydrazines with Thiols.

The sulfonylation method stands out as a simple and efficient approach for synthesizing sulfonamides. Despite the advancements in constructing the sulfonamide framework, the potential use of phenyl hydrazine as an amination source remains unexplored. Herein, we report a metal-free, environment-friendly photoredox-catalyzed sulfonylation of phenylhydrazines using thiols, employing MeCN:H2O as a green solvent and eosin Y as a photoredox catalyst. This strategy exhibits a broad substrate scope and good functional group compatibility, including hetero(aryl) as well as aliphatic phenylhydrazines. Finally, this protocol also demonstrated good application for the synthesis of pharmaceutical analogues.

Visible-light-induced C-S bond formation in the synthesis of 2,4-disubstituted thiazoles through cascade difunctionalization of acetophenone: a greener approach.

A groundbreaking approach has been developed for synthesizing 2,4-disubstituted thiazoles using an eco-friendly and metal-free approach. This novel method utilizes methyl aryl ketones, N-bromo-succinimide (NBS), and thioamides in water as a green reaction medium under visible light irradiation. Using NBS as a bromine source, the reaction takes place through an in situ α-bromination method. This approach does not require any catalyst, which makes it exceptionally beneficial for the environment. The advantages of this efficient approach are manifold and include the use of greener conditions, absence of metals, easy isolation of products, cost-effectiveness, non-toxicity, and reliance on renewable energy sources like visible light. Moreover, this technique offers higher product purity and excellent yield, enhancing itsappeal.

Photoinduced, Metal-Free Hydroacylation of Aromatic Alkynes for Synthesis of α,ß-Unsaturated Ketones via C(sp3)-H Functionalization.

Despite the notable advancements made over the past decade in achieving carbon-carbon bonds by transition-metal-catalyzed cross-coupling processes, metal-free cross-coupling reactions for hydroacylation of aromatic alkynes via C(sp3)-H functionalization are still rare and highly desired. Here we report a metal-free reliable approach for the synthesis of α,ß-unsaturated ketones (chalcones) via C(sp3)-H functionalization using MeCN:H2O as green solvent, Eosin Y as organic photocatalyst, and ambient air as oxidant. More significantly, this strategy can effectively transform a variety of methyl arenes and aromatic alkynes into the desired product. With high atom efficiency, use of green solvents, metal-free nature, environmental friendliness, and visible light as a renewable energy source, this method is compatible with biologically active molecules.

Photo-triggered C-arylation of active-methylene compounds with diazonium salts via an electron donor-acceptor (EDA) complex.

The elucidation of the C-arylation of active methylene compounds under visible light conditions without a photocatalyst presents an intellectual challenge. The photo-induced C-arylation of active methylene compounds via electron donor-acceptor (EDA) complexes shows a strategic path for the synthesis of pharmacologically relevant compounds. This expansive and efficacious methodology facilitates C-arylation under environmentally conscientious conditions, exhibiting exemplary compatibility with diverse functional groups and yielding numerous compounds. This environmentally sustainable transformation underscores the merits of the procedural simplicity and benign reaction conditions. Notably, all resultant products were judiciously derived from active methylene compounds and diazonium salts through the intermediacy of the EDA complex.

Microwave-assisted chemoselective transamidation of secondary amides by selective N-C(O) bond cleavage under catalyst, additive and solvent-free conditions.

A microwave-assisted, highly chemoselective protocol has been developed for the transamidation of tert-butyloxycarbonyl (Boc) activated secondary carboxamides with amines. Under non-conventional microwave techniques, the reactions were achieved under catalyst, additive, promoter and solvent-free conditions. The transamidation of a structurally diverse set of amides and amines was accomplished in good to excellent yields. The salient features of the developed methodology include a simple operation, broad substrate scope, functional group tolerance, practicality, and the scalability.

Synthesis of phenylethanoid glycosides from acrylic esters of glucose and aryldiazonium salts via palladium-catalyzed cross-coupling reactions and evaluation of their anti-Alzheimer activity.

Cinnamic acid-containing sugar compounds such as phenylethanoid glycosides are widely present in nature and display various biological activities. In this work, the synthesis of trans-cinnamic acid containing phenylethanoid glycosides was achieved via palladium-catalyzed cross-coupling reactions between glycosyl acrylic esters and aryldiazonium salts. A wide range of functionalized aryldiazonium salts were successfully coupled with 6-O- and 4-O-acrylic esters of glucose under optimized conditions. The reactions proceeded at room temperature in the absence of additives and base. The desired products were obtained in good to excellent yields. Selected compounds from the library were screened for anti-Alzheimer activity, while compound 16 displayed significant inhibitory activities against butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) enzymes.

Electro-organic green synthesis of dicyano-2-(2-oxoindolin-3-ylidene) malononitriles using molecular iodine as catalyst.

The first electrochemical molecular iodine promoted, domino reactions for the green synthesis of biologically relevant dicyano 2-(2-oxoindolin-3-ylidene) malononitriles (11 examples, up to 94% yield) from readily available isatin derivatives, malononitrile, and iodine at room temperature have been presented. This synthesis method showed tolerance towards various EDG and EWG and was completed in a short reaction time at the constant low current density of 5 mA cm-2 in the low redox potential range of -0.14 to 0.07 V. The present study exhibited by-product-free formation, easy operation, and product isolation. In particular the formation of a C[double bond, length as m-dash]C bond was observed at room temperature with a high atom economy. Furthermore, in the present study, the electrochemical behavior of dicyano 2-(2-oxoindolin-3-ylidene) malononitrile derivatives using a cyclic voltammetry (CV) technique in 0.1 M NaClO4 in acetonitrile solution was studied. All the chosen substituted isatin exhibited well-defined diffusion-controlled quasi-reversible redox peaks except 5-substituted derivatives. This synthesis could serve as an alternative strategy to synthesize other biologically important oxoindolin-3-ylidene malononitrile derivatives.

A green synthesis of pyrimido[4,5-b]quinolines and pyrido[2,3-d]pyrimidines via a mechanochemical approach.

A cost-effective and competent approach has been established for the synthesis of pyrimido[4,5-b]quinolines and pyrido[2,3-d]pyrimidines via a multicomponent reaction of 1,3 diketones (dimedone, barbituric acid, and Meldrum's acid), 6-aminouracil and aromatic aldehyde, through mechanochemical synthesis using a ball-mill. This transformation involves a one pot, catalyst-free, and solvent-free pathway to develop the desired products under mild reaction conditions.

Visible-light-absorbing C-N cross-coupling for the synthesis of hydrazones involving C(sp2)-H/C(sp3)-H functionalization.

An efficient C-N cross-coupling approach for the synthesis of hydrazones was developed through C(sp2)-H and C(sp3)-H functionalization of indole and methylarene under visible light irradiation using photocatalyst eosin Y, ethanol:water as a green solvent and atmospheric air as an oxidant. With the aid of eosin Y, the C-H bonds of indole and methylarenes were activated followed by coupling with arylhydrazines. The procedure was applied to a wide variety of substrates with good functional group compatibility, offering a creative way to make hydrazones from inexpensive and easily accessible raw materials. The absence of metals, low cost, environmental friendliness, green solvent, non-toxicity, ease of handling, and utilization of renewable energy sources like visible light are some of this method's primary advantages.

Urea hydrogen peroxide-initiated synthesis of pyranopyrazoles through oxidative coupling under base- and metal-free conditions by physical grinding method.

A novel multicomponent one-pot expeditious synthesis of highly functionalized and pharmaceutically fascinated pyranopyrazoles has been developed. This reaction occurs via tandem Knoevenagel condensation reaction of methyl aryl derivatives, 3-methyl pyrazolone and malononitrile in the presence of urea hydrogen peroxide under the physical grinding method. The present methodology offers several benefits such as available green and cheap starting materials, solvent-free, mild reaction conditions, high atom economy, eco-friendly standards, excellent yields and easy isolation of the products without column chromatographic separation.

A facile and efficient multicomponent ultrasound-assisted "on water" synthesis of benzodiazepine ring.

A facile and efficient multicomponent synthesis of benzodiazepine ring in water under ultrasound irradiation is reported first time. The current procedure escapes traditional chromatography and purification process and provided the product in excellent yields of 95% as compared to conventional methods. The approach was also validated on gram-scale synthesis.

Eosin Y-Catalyzed Synthesis of 3-Aminoimidazo[1,2-a]Pyridines via the HAT Process under Visible Light through Formation of the C-N Bond.

A comfortable, environment-friendly, and metal-free approach for synthesizing the biologically important moiety aminoimidazopyridine through the multicomponent reaction of benzylamine, 2-aminopyridine, and t-butyl isocyanide under visible light using eosin Y as a photocatalyst has been developed. Inexpensive, nontoxic, the effortless accessibility of starting materials, and nonparticipation of particular glassware and a photoreactor system are important qualities of the current approach. Strangely, the mild conditions, environment-friendly, and enumerating tolerance of an extensive range of both electron-donating and electron-withdrawing groups are additional features of the approach.

Lemon juice catalyzed C-C bond formation via C-H activation of methylarene: a sustainable synthesis of chromenopyrimidines.

An economical and proficient approach has been developed for the synthesis of chromenopyrimidines via three-component reaction of thiobarbituric acid/barbituric acid, methylarenes and dimedone/1,3-cyclohexanedione by using lemon juice as a natural, biodegradable catalyst and TBHP as an oxidant. This transformation involves metal-free C-C bond formation via C-H activation of methylarenes under mild reaction conditions.