Palladium-Catalyzed Oxidative <i>N</i>‑Dealkylation/Carbonylation of Tertiary Amines with Alkynes to α,β-Alkynylamides

The first highly effective Pd/C-catalyzed oxidative <i>N</i>-dealkylation/carbonylation of various aliphatic as well as cyclic tertiary amines with alkynes has been described. The selective sp³ C–N bond activation of tertiary amines at the less steric side using O₂ as a sole oxidant and a plausible reaction pathway for the reaction are discussed. The general and operationally simple methodology provides an alternative for the synthesis of a wide range of alk-2-ynamide derivatives under mild conditions. The present protocol is ecofriendly and practical, and it shows significant recyclability

Pd/C-Catalyzed Aminocarbonylation of Aryl Iodides via Oxidative C–N Bond Activation of Tertiary Amines to Tertiary Amides

This work reports oxidative <i>N</i>-dealkylation/carbonylation of tertiary amines to tertiary amides by using molecular oxygen as a sole oxidant using a Pd/C catalyst. This protocol is free from ligands, additives, bases, and cocatalysts. Different tertiary amines as well as aryl iodides have been examined for this transformation, providing desired products in good to excellent yield

Cobalt Ferrite Nanocrystallites for Sustainable Hydrogen Production Application

Cobalt ferrite, CoFe2O4, nanocrystalline films were deposited using electrostatic spray method and explored in sustainable hydrogen production application. Reflection planes in X-ray diffraction pattern confirm CoFe2O4 phase. The surface scanning microscopy photoimages reveal an agglomeration of closely-packed CoFe2O4 nanoflakes. Concentrated solar-panel, a two-step water splitting process, measurement technique was preferred for measuring the hydrogen generation rate. For about 5 hr sustainable, 440 mL/hr, hydrogen production activity was achieved, confirming the efficient use of cobalt ferrite nanocrystallites film in hydrogen production application

Amine-Functionalized Graphene Oxide-Stabilized Pd Nanoparticles (Pd@APGO): A Novel and Efficient Catalyst for the Suzuki and Carbonylative Suzuki–Miyaura Coupling Reactions

Palladium nanoparticles (NPs) are decorated on the surface of an amine-functionalized graphene oxide (Pd@APGO) and characterized by using various analytical techniques. In this methodology, the surface of graphene oxide is modified using the amine functional groups which help stabilization and distribution of Pd NPs very well and increases the surface electron density of NPs by electron donating from amine groups. This developed catalyst shows a high catalytic activity toward the Suzuki coupling and carbonylative Suzuki–Miyaura coupling reactions at mild reaction conditions. The amine on the graphene oxide plays a very crucial role to stabilize and increase the electron density of Pd NPs and prevents the leaching of Pd metals. The Pd@APGO catalyst showed excellent catalytic activity (>90%) with a large range of substrates for both of the reactions and provides five recycle runs without the loss of its activity

Synthesis of an adenine nucleoside containing the (8'R) epimeric carbohydrate core of amipurimycin and its biological study

The (8'R) epimeric carbohydrate core 2 of amipurimycin was synthesized from D-glucose derived allylic alcohol 3 in 11 steps and 13% overall yield. The key steps involve an acid-catalyzed acetonide ring opening of 9 with concomitant formation of an unprecedented pyranose ring skeleton to give 2,7-dioxabicyclo[3.2.1]octane 10. The α-orientation of the furan ring in 10 readily allows the stereoselective β-glycosylation and opening of the furanose ring that on removal of protecting groups affords the pyranosyl adenine nucleoside 2. The antifungal and anticancer activities of 2 were studied

Synthesis of anomeric 1,5-anhydrosugars as conformationally locked selective α-mannosidase inhibitors

Anomeric 1,5-anhydrosugar 2 was synthesized from D-glucose derived N-Cbz protected aminodiol 8. The key step involves, acid catalyzed hydrolysis of 1,2-acetonide group in 8 to get hemiacetal that concomitantly undergoes formation of the pyranose ring by attack of C-3 hydroxyethyl group on anomeric C-1, leading to the formation of dioxabicyclo[3.2.1]octane skeleton which on hydrogenolyis gave 2. The glycosidase inhibitory activities of hydroxy- and amino-substituted anomeric 1,5-anhydrosugars 1 and 2, respectively, showed selective inhibition of α-mannosidase. These results were substantiated by molecular docking studies using WHAT IF software and AUTODOCK 4.0 program

Theoretical and Experimental Investigation of Palladium(II)-Catalyzed Decarboxylative Addition of Arenecarboxylic Acid to Nitrile

The reaction mechanism of palladium­(II)-catalyzed decarboxylative addition of 2,6-dimethoxybenzoic acid to acetonitrile was investigated by means of density functional theory (DFT) calculations. Calculations of the free energy profile for decarboxylation and carbopalladation indicated carbopalladation as the rate-determining step of the reaction. Investigation of the free energy profile for a series of experimentally evaluated nitrogen-based bidentate palladium ligands revealed that higher energy is required for decarboxylation and carbopalladation employing the experimentally least efficient ligand. The DFT investigation also showed that the relative free energies of the transition states were lowered in polar solvent, and preparative experiments confirmed that a nonoptimal ligand could be greatly improved by addition of water to the reaction system

Extraction and separation of mercury(II) from succinate media with high molecular weight amine as an extractant

The extraction of mercury(II) from succinate solutions by 2-octylaminopyridine (2-OAP) has been studied by metal distribution measurements. The optimum extraction conditions were determined from a critical study of effects of pH, sodium succinate concentration and 2-octylaminopyridine concentration. The probable composition of the species has been deduced from log–log plots. The extraction reaction proceeds with ion-pair formation and the stoichiometry of extracted species was found to be [(2OAPH+)2 Hg(Succinate)22−](org). The method has been used to separate mercury(II) from commonly associated elements. The method has been further extended to separate and to estimate mercury in synthetic mixtures and real samples