87613-34-1

Upstream product

• 87613-31-8 N-Methyl-N-phenyl-N'-[1-phenyl-1-(5-phenyl-isoxazol-3-yl)-meth-(E)-ylidene]-hydrazine 
• 3558-24-5 1-methyl-2-phenyl-1H-indole 
• 67-68-5 dimethyl sulfoxide 
• 123-39-7 N-Methylformamide 
• 938305-58-9 (1-methyl-2-phenyl-1H-indol-3-yl)methanamine 
• 1355659-10-7 N-methyl-1-(1-methyl-2-phenyl-1H-indol-3-yl)methanamine 
• 1355652-35-5 N-((1-methyl-2-phenyl-1H-indol-3-yl)methylene)methanamine 
• 1354817-33-6 N-((1-methyl-2-phenyl-1H-indol-3-yl)methyl)formamide 
• 859965-07-4 (E/Z)-1-methyl-2-phenyl-1H-indole-3-carbaldehyde oxime 
• 68-12-2 N,N-dimethyl-formamide 
• 1757-72-8 1-methyl-2-phenyl-1H-indole-3-carbaldehyde 
• 55305-43-6 N-cyano-N-phenyl-p-toluenesulfonamide 
• 140-29-4 phenylacetonitrile 
• 521984-94-1 1-methyl-2-phenyl-1H-pyrrolo-[2,3-b]pyridine 

Downstream Products

• 59050-41-8 2-phenyl-1-methylindole-3-carboxylic acid 
• 1600501-10-7 11-methyl-6-(p-tolyl)-11H-indolo[3,2-c]quinoline 

Relevant academic research and scientific papers

Dihalo(imidazolium)sulfuranes: A Versatile Platform for the Synthesis of New Electrophilic Group-Transfer Reagents

The syntheses of imidazolium thiocyanates and imidazolium thioalkynes from dihalo(imidazolium) sulfuranes are reported and their reactivities as CN+ and R-CC+ synthons evaluated, respectively. The easy and scalable preparation of these electrophilic reagents, their operationally simple handling, broad substrate scope, and functional group tolerance clearly illustrate the potential of these species to become a reference for the direct electrophilic cyanation and alkynylation of organic substrates.

Site-Selective Electrochemical C-H Cyanation of Indoles

An electrochemical approach for the site-selective C-H cyanation of indoles employing readily available TMSCN as cyano source has been developed. The electrosynthesis relies on the tris(4-bromophenyl)amine as a redox catalyst, which achieves better yield and regioselectivity. A variety of C2- and C3-cyanated indoles were obtained in satisfactory yields. The reactions are conducted in a simple undivided cell at room temperature and obviate the need for transition-metal reagent and chemical oxidant.

DIBENZOTHIOPHENE SALT AS ALKYNYLATING AND CYANATING AGENT

The present invention describes a new alkynylation and cyanation agent, as well as its preparation and use to introduce nitrile (cyano) or alkyne groups into chemical target molecules by means of an electrophilic reaction. To enable an electrophilic reaction, the chemical backbone of dibenzothiophene was used.

5-(Cyano)dibenzothiophenium Triflate: A Sulfur-Based Reagent for Electrophilic Cyanation and Cyanocyclizations

The synthesis of 5-(cyano)dibenzothiophenium triflate 9, prepared by activation of dibenzo[b,d]thiophene-5-oxide with Tf2O and subsequent reaction with TMSCN is reported, and its reactivity as electrophilic cyanation reagent evaluated. The scalable preparation, easy handling and broad substrate scope of the electrophilic cyanation promoted by 9, which includes amines, thiols, silyl enol ethers, alkenes, electron rich (hetero)arenes and polyaromatic hydrocarbons, illustrate the synthetic potential of this reagent. Importantly, Lewis acid activation of the reagent is not required for the transfer process. We additionally report herein biomimetic cyanocyclization cascade reactions, which are not promoted by typical electrophilic cyanation reagents, demonstrating the superior ability of 9 to trigger challenging transformations.

GaCl3-Catalyzed C-H Cyanation of Indoles with N-Cyanosuccinimide

An efficient GaCl3-catalyzed direct cyanation of indoles and pyrroles using bench-stable electrophilic cyanating agent N-cyanosuccinimide was achieved and afforded 3-cyanoindoles and 2-cyanopyrroles in good yields and excellent regioselectivities. Notably, this protocol exhibited high reactivity for unprotected indoles and was applicable to a broad range of indole and pyrrole substrates.

Palladium-Catalyzed Late-Stage Direct Arene Cyanation

Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.

An insight on the influence of surface Lewis acid sites for regioselective C–H bond C3-cyanation of indole using NH4I and DMF as combined cyanide source over Cu/SBA-15 catalyst

The Cu dispersed on mesoporous SBA-15 has demonstrated the regioselective C–H bond C3-cyanation of indoles by in-situ generation of –CN using DMF and NH4I in presence of O2. Pyridine adsorbed diffuse reflectance infrared spectroscopy (DRIFTS) results revealed that surface Cu2+ species are acting as Lewis acid sites in the in-situ generation of cyano- group for the synthesis of indole nitriles. A direct correlation between Cu metal surface area and the indole nitrile yields are established and the dual role of copper is substantiated by N2O titration and XPS techniques. The 10 wt%Cu/SBA-15 demonstrated superior performance when compared to Pd, Ru supported on SBA-15. The 10 wt%Cu/SBA-15 catalyst showed consistent activity and selectivity after the 4th cycle.

SUBSTITUTED IMIDAZOLIUM SULFURANES AND THEIR USE

The present invention refers to substituted imidazolium sulfuranes, the use thereof for the transfer of a -CN group or an alkyne group.

A facile and efficient synthesis of 3-cyanoindoles by a simple palladium(II)-catalyzed C─H activation of indoles

An efficient trans-PdCl2(NH2CH2COOH)2-catalyzed direct C3-cyanation of indole C─H bonds is described. Notably, free (N─H)-indoles reacted smoothly using the procedure, and the desired product 3-cyanoindoles were obtained in good to excellent yields.

Copper-Catalyzed Acyloxycyanation of Alkynes with Acetonitrile: Regioselective Construction of Cyclic Acrylonitriles by 6-endo or 5-exo Cyclization

An efficient difunctionalization of alkynes by tandem iodolactonization and copper-catalyzed cyanation using acetonitrile as a cyanating reagent is reported for the first time. This approach can afford cyano-containing isocoumarin or phthalide derivatives