Skeletal Editing through Molecular Recombination of 2H-Indazoles to Azo-Linked-Quinazolinones.

A new protocol by the combinatory use of two equivalent of indazoles starting material with one being the carbon source via its C3-reactivity and the other, the coupling partner has been developed for the selectfluor-mediated single atom skeletal editing of 2H-indazoles. The azo-linked-2,3-disubstituted quinazolin-4-one derivatives were obtained through a carbon atom insertion between the two nitrogens of the indazole ring and simultaneous oxidation at C3 position of both indazole moieties. Mechanistic investigations reveal that the amidic carbonyl oxygen of the product is derived from water and the reaction proceeds through in-situ generated N-centred indazolone radical intermediate.

An Electrochemical Oxo-amination of 2H-Indazoles: Synthesis of Symmetrical and Unsymmetrical Indazolylindazolones.

We have established a supporting-electrolyte free electrochemical method for the synthesis of indazolylindazolones through oxygen reduction reaction (eORR) induced 1,3-oxo-amination of 2H-indazoles where 2H-indazole is used as both aminating agent as well as the precursor of indazolone. Moreover, we have merged indazolone and indazole to get unsymmetrical indazolylindazolones through direct electrochemical cross-dehydrogenative coupling (CDC). This exogenous metal-, oxidant- and catalyst-free protocol delivered a number of multi-functionalized products with high tolerance of diverse functional groups.

One-Pot Manganese (I)-Catalyzed Oxidant-Controlled Divergent Functionalization of 2-Arylindazoles.

The oxidant-controlled divergent synthesis of C-2' formyl 2H-indazoles and indazoloindazolediones has been developed through Mn(I)- catalyzed ortho C-H functionalization of 2H-indazoles with para-formaldehyde to afford C-2' hydroxymethylated 2H-indazoles and subsequently oxidation with varying the amount of DDQ in one-pot. By employing selectfluor as the oxidant instead of DDQ, this reaction exclusively provided indazolebenzoxazine derivatives. This strategy delivered unsymmetrical indazoloindazoledione and indazolobenzoxazine with varied functional group tolerance in moderate to good yields.

Silylation of 2H-indazoles by photoinduced hydrogen atom transfer catalysis.

A metal-free, visible-light-mediated C-H silylation of 2H-indazoles with triphenylsilane has been developed employing 4CzIPN as a photocatalyst and triisopropylsilanethiol as a hydrogen atom transfer (HAT) reagent under aerobic reaction conditions. This method shows tolerance toward many functional groups and affords a variety of silylated indazoles at up to 89% yield. The experimental results suggest that the reaction progresses through a radical pathway.

Visible Light Induced Three-Component 1,2-Dicarbofunctionalization of Alkenes and Alkynes.

Harnessing visible-light in organic synthesis is one of the most effective methods that aligns with green and sustainable chemistry principles and hence skyrocketed in the last two decades. Similarly, three-component 1,2-dicarbofunctionalization of alkenes and alkynes has recently been a great choice to construct complex molecular systems in an easy and rapid manner. Therefore, light-induced reactions can be an excellent alternative to carry out 1,2-dicarbofunctionalization reactions, and very recently, organic chemists across the globe have fascinated us with their interesting articles. In this present review, we have summarized the recent advancements in the area of visible light induced three-component 1,2-dicarbofunctionalization of alkenes and alkynes till March 2023. We have categorized the discussion based on the catalysts used to carry out the transformations for better understanding and different important aspects of these transformations have also been covered.

Recent advances in carbosilylation of alkenes and alkynes.

Alkene and alkyne difunctionalization is a flexible process that allows the construction of two functional groups simultaneously in one step. On the other hand, carbosilylation, an ingenious difunctionalization pathway to concurrently incorporate both a silyl group and an organic functional group (alkyl, (hetero)aryl, alkenyl, alkynyl and allenyl) across a carbon-carbon multiple-bond system, is achieving immense interest in recent days. This review article provides a decade's update on the discoveries and developments in the synthesis of carbosilylated products from two very important carbon-carbon unsaturated substrates, alkenes and alkynes.

Visible-light-induced cascade reaction: a sustainable approach towards molecular complexity.

Photoredox catalysis has demonstrated rapid evolution in the field of synthetic organic chemistry. On the other hand, the splendour of cascade reactions in providing complex molecular architectures renders them a cutting-edge research area. Therefore, the merging of photocatalysis with cascade synthesis brings out a synthetic paradigm with immense potential. The development of photocascade catalysis for a target molecule with a particular molecular skeleton and stereochemical framework presents certain challenges but provides a robust and environmentally benign synthetic alternative. This comprehensive review assembles all the accomplishments and highlights of visible-light-induced cascade reactions with literature coverage up to October 2022.

Ortho C-H Functionalizations of 2-Aryl-2H-Indazoles.

C-H Functionalization is ubiquitously considered as a powerful, efficient and handy tool for installing various functional groups in complex organic heterocycles in an easier and step-economic way. Similarly, indazole is endowed as a potent heterocycle and is eminent for its profound impact in biological, medicinal and industrial chemistry. In this scenario, C-H functionalization at the selective ortho position of 2-arylindazole in assistance of a metal catalyst is also becoming an appealing approach in synthetic organic chemistry. This review addressed the recent findings and developments on ortho C-H functionalization of 2-aryl-2H-indazazoles with literature coverage extending from 2018 to May 2022.

Ortho C-H Functionalization of 2-Arylimidazo[1,2-a]pyridines.

C-H activation and functionalization is quite promising in recent days as the strategy offers a go-to general method for different bond formations and hence grants synthetic versatility. At the same time, imidazopyridine, a fused bicycle of imidazole moiety with pyridine ring, has a profound impact due to its ubiquitous and prodigious application in medicinal as well as material chemistry. The presence of N-1 atom in 2-arylImidazo[1,2-a]pyridine facilitates the coordination with metal catalysts leading to the formation of ortho-substituted products. This review summarizes all the articles on ortho C-H functionalization of 2-arylImidazo[1,2-a]pyridines published till August 2021.

Synthesis of Unsymmetrical Biheteroarenes via Dehydrogenative and Decarboxylative Coupling: a Decade Update.

The design and development of robust and efficient methods for installing one heterocycle with another is endowed as a ubiquitous and powerful synthetic strategy to access complex organic biheterocycles in recent days due to their pervasive applications in medicinal as well as material chemistry. This perspective presents an overview on the recent findings and developments for the synthesis of unsymmetrical biheteroarenes via dehydrogenative and decarboxylative couplings with literature coverage mainly extending from 2011 to 2021. For simplification of the readers, the article has been subcategorized based on the catalysts used in the reactions.

Organocatalytic Oxidative C-H Amination of Aldehyde Hydrazones with Azoles at Ambient Temperature.

An efficient, metal-free, and direct oxidative amination of aldehyde-derived hydrazones with azoles has been developed using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as an organocatalyst at ambient temperature. This protocol provides a wide range of aminated hydrazone derivatives in a step and atom economical fashion. The reaction possibly follows a radical mechanism.

Asymmetric C(sp3)-H borylation: an update.

Chiral organoboronates have emerged as a key intermediate in the development of pharmaceuticals and materials science. Therefore, several attempts have been made to design various synthetic methods to easily furnish these compounds during the past few decades. Inter alia, asymmetric catalysis has been increasing rapidly as a viable, practical and beneficial strategy for their preparation. In this respect, recent years have witnessed significant progress in aliphatic C-H borylation as the generated carbon-boron bonds are largely utilized to produce other carbon-carbon, carbon-nitrogen and carbon-oxygen bonds. This review presents a detailed overview and analysis of transition metal-catalyzed asymmetric C(sp3)-H borylation strategies. Overall, it assembles all the recent developments in this particular synthetic avenue up to March 2022.

Transition-metal-catalyzed ortho C-H functionalization of 2-arylquinoxalines.

Recently, direct C-H bond activation and functionalization has become a prodigious and hot topic among synthetic organic chemists due to its step-economic nature and substantial synthetic versatility. On the other hand, quinoxaline, a fused bicycle of benzene and pyrazine, has omnipresent applications in medicinal-, industrial- and materials chemistry. The presence of the N-1 atom in 2-arylquinoxaline enables chelation formation with a metal catalyst leading to the formation of ortho-substituted products. In this review, all articles related to the ortho C-H bond functionalization of 2-arylquinoxalines published up to May 2022 are highlighted.

Hypervalent iodine(III)-mediated oxidative dearomatization of 2H-indazoles towards indazolyl indazolones.

A new iodine(III)-mediated oxidative dearomatization of 2H-indazoles has been developed to afford N-1 indazolyl indazolones. In this methodology, PIFA plays a dual role: as an oxidant and as a carbonyl oxygen source. A series of indazolone derivatives was promptly synthesized in good to excellent yields through sequential C-heteroatom bond formation. Mechanistic studies indicate that the reaction likely takes place through an SET pathway.

Fluorination of 2H-Indazoles Using N-Fluorobenzenesulfonimide.

An efficient, simple, and metal-free fluorination of 2H-indazoles has been developed using N-fluorobenzenesulfonimide (NFSI) in water under ambient air. This transformation provides direct access to fluorinated indazole derivatives with broad functionalities in satisfactory yields. The experimental results suggest a radical mechanistic pathway of this protocol.

Potassium Persulfate Mediated Chemodivergent C-3 Functionalization of 2H-Indazoles with DMSO as C1 Source.

A facile, efficient, and transition-metal-free chemodivergent C-3 functionalization of 2H-indazoles was developed under aerobic conditions using carboxylic acid and DMSO as the combined source of the carboxylic acid ester group and DMSO as the formylating agent. A series of formylated indazoles and carboxylic acid esters of indazole derivatives were produced in moderate to excellent yields. The mechanistic studies suggest that the reactions probably proceed through a radical pathway.

Ru(II)-Catalyzed Switchable C-H Alkylation and Spirocyclization of 2-Arylquinoxalines with Maleimides via ortho-C-H Activation.

A Ru(II)-catalyzed facile and controllable protocol for C-H alkylation and spirocyclization of 2-arylquinoxalines with maleimides has been achieved under ambient air in high yields. Sequential ortho-C-H activation and C-annulation results in the formation of diverse polyheterocycles containing spiro[indeno[1,2-b]quinoxaline-11,3'-pyrrolidine]-2',5'-diones, which are of potent interest in medicinal chemistry. Mechanistic investigations suggest a reversible cleavage of the ortho-C-H bond in the turnover-limiting step.

Light-induced borylation: developments and mechanistic insights.

Organoboron compounds are very important derivatives because of their profound impacts on medicinal, biological as well as industrial applications. The development of several novel borylation methodologies has achieved momentous interest among synthetic chemists. In this scenario, eco-friendly light-induced borylation is progressively becoming one of the best synthetic tools in recent days to prepare organoboronic ester and acid derivatives based on green chemistry rules. In this article, we have discussed all the UV- and visible-light-induced borylation strategies developed in the last decade. Furthermore, special attention is given to the mechanisms of these borylation methodologies for better understanding of reaction insights.

Visible-light-induced silylation: an update.

Visible-light-driven functionalization of various organic systems has proved to be extremely successful and reached an impressive level of sophistication as well as efficiency in the last two decades. At the same time, organosilicon compounds are significant due to their promising applications in therapeutic agents, drug delivery, building blocks and so on. More interestingly, they are cheap, operationally simple, highly stable, less toxic and easy to handle. In this scenario, an environment-friendly synthetic approach for silylation, such as visible-light-induced silylation, is in high demand at present for molecule construction having the C-Si bond. This perspective summarizes the recent findings and developments in the emerging area of photocatalytic silylation with literature coverage mainly extending from 2014 to February 2021.

Rhodium-Catalyzed Directed C(sp2)-H Bond Addition of 2-Arylindazoles to N-Sulfonylformaldimines and Activated Aldehydes.

Rhodium-catalyzed directed C-H functionalization of 2-arylindazoles with N-sulfonylformaldimines has been developed to provide a variety of N-benzylarylsulfonamide derivatives with good to excellent yields. Different activated aldehydes like ethyl glyoxalate and 2,2,2-trifluoroacetaldehyde also efficiently underwent nucleophilic addition with 2-arylindazoles. These selective transformations occur through the control of C3 nucleophilicity of indazole moiety. Mechanistic studies suggest that C-H activation step may be a rate-limiting step.