Ru (III) Schiff‐base complex anchored on nanosilica as an efficient and retrievable catalyst for hydration of nitriles

Transition metal catalyzed hydration of nitriles is an attractive methodology for amide synthesis, and hence recently attracted wide attention. It is one of the significant organic transformations as amides play a vital role in biological, pharmaceutical and industrial applications. In this work, we report the synthesis of a new solid supported Ru (III) Schiff base complex, Ru@imine‐nanoSiO₂ immobilized on nanosilica obtained from rice husk. The complex was characterized by FTIR, powder X‐ray diffraction, BET surface area measurement, UV–vis, SEM–EDX, TEM, ESR, X‐ray photoelectron spectroscopy and ICP‐AES analysis. Using Ru@imine‐nanoSiO₂ as the catalyst, the hydration of nitriles in i‐PrOH at 40 °C was studied which resulted in good isolated yields (60–99%). The catalyst can be recycled and reused up to 5^th cycle without any loss in activity. The products were characterized by FTIR, GC–MS and ¹H‐NMR spectroscopy and compared with authentic samples.     

Uniform silver nanoparticles on tunable porous N‐doped carbon nanospheres for aerobic oxidative synthesis of aryl nitriles from benzylic alcohols

Tunable N‐doped carbon nanospheres from sucrose as carbon source and Tris(2‐aminoethyl)amine (TAEA) as nitrogen source by a simple and easily reproducible method were prepared. It was demonstrated that the tunable N‐doping of carbon spheres could be realized by altering the ratio of TAEA in the raw materials. The content of doped nitrogen, surface area, pore volume and pore size of carbon nanospheres were increased with the increasing of TAEA amount in the hydrothermal process. Prepared N‐doped carbon nanospheres act as solid ligand for anchoring of Ag NPs which generated via chemical reduction of Ag ions. Benzylic alcohols and aldehydes were converted into the aryl nitriles by using Ag/N‐CS‐1 nanospheres as the catalyst and O₂ as the oxidant, efficiently. This catalyst was stable and could use for 6 successful runs.     

Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles

Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.     

Y(OTf)3‐Catalyzed,One‐Pot Synthesis of 1,2,4‐Oxadiazole Derivatives

Direct one‐step synthesis of 1,2,4‐oxadiazole from ketones, nitriles, and nitric acid is described using yttrium triflate [Y(OTf)₃] as the catalyst. The salient features of this method include a simple procedure, mild condition, easy purification, and good yields.     

Silica-bonded S-sulfonic acid: an efficient and recyclable solid acid catalyst for the three-component synthesis of α-amino nitriles

Silica-bonded S-sulfonic acid (SBSSA) is employed as a recyclable catalyst for the synthesis of α-amino nitriles. These syntheses were performed via a one-pot three-component condensation of aldehydes, amines, and trimethylsilyl cyanide under mild reaction conditions at room temperature.     

An N-Trifluoromethylation/Cyclization Strategy for Accessing Diverse N-Trifluoromethyl Azoles from Nitriles and 1,3-Dipoles

N-Trifluoromethyl azoles are valuable targets in medicinal chemistry, but their synthesis is challenging. Classical preparation of N-CF₃ azoles relies on the functional group interconversions but suffers from tedious N-pre-functionalization and unfriendly agents. Introduction of the CF₃ onto the nitrogen of heterocycles provides a direct route to such motifs, but the N-trifluoromethylation remains underdeveloped. Reported here is an alternative and scalable cyclization strategy based on NCF₃-containing synthons for constructing N-CF₃ azoles. The approach involves the N-trifluoromethylation of nitriles followed by a [3+2] cyclization between resulting N-CF₃ nitrilium derivatives and 1,3-dipoles. PhICF₃Cl was an effective CF₃ source for the transformation. As a result, a generic platform is established to divergently synthesize N-trifluoromethylated tetrazoles, imidazoles, and 1,2,3-triazoles by using sodium azide, activated methylene isocyanides, and diazo compounds as dipoles.     

Preparation of Polyfunctionalized Aromatic Nitriles from Aryl Oxazolines

A selective ortho,ortho’-functionalization of readily available aryl oxazolines by two successive magnesiations with sBu₂Mg in toluene followed by trapping reactions with electrophiles, such as (hetero)aryl iodides or bromides, iodine, tosyl cyanide, ethyl cyanoformate or allylic bromides (39 examples, 62–99 % yield) is reported. Treatment of these aryl oxazolines with excess oxalyl chloride and catalytic amounts of DMF (50 °C, 4 h) provided the corresponding nitriles (36 examples, 73–99 % yield). Conversions of these nitriles to valuable heterocycles are reported, and a tentative mechanism is proposed.     

Microwave Assisted,Solvent Free One Pot Synthesis of Nitriles from Aryl Aldehydes on Melamin Formaldehyde as Solid Support

Various aryl aldehydes underwent prompt one pot conversion into the corresponding nitriles in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation in the presence of ammonium acetate as catalyst.