Multicomponent Synthesis of S-Benzyl Dithiocarbamates from para-Quinone Methides and Their Biological Evaluation for the Treatment of Alzheimer's Disease.

Multicomponent synthesis of biologically relevant S-benzyl dithiocarbamates from para-quinone methides, amines, and carbon disulfide are described under catalyst and additive-free conditions. The reactions proceeded at room temperature in a short span of time with excellent yields. One of the synthesized compounds, 3e showed considerable acetylcholinesterase (AChE) inhibitory (51.70 + 5.63% at 20 µm) and antioxidant (63.52 ± 1.15 at 20 µm) activities.

C2 -Symmetric Bissulfoximine-Based Metal Complexes: Synthesis, Characterization and Their Electrocatalytic Activity in Oxygen Reduction Reaction.

Sulfoximine-based metal complexes have gained much interest in recent years owing to their promising properties in synthetic organic chemistry. These sulfoximines have been recently introduced in the field of organometallics. However, the coordination properties of pincer sulfoximine ligands and their metal complexes have not been reported. Here, a C2 -symmetric bissulfoximine-based pincer ligand ((pyridine-2,6-diylbis(methylene))bis(azaneylylidene))bis(diphenyl-λ6 -sulfanone), namely S-P ligand and its metal [M(SP)2 ]2+ {M=Fe (SC-1), Co (SC-2), Ni (SC-3), Cu (SC-4)} complexes, were synthesized. The complexes were characterized by different spectroscopic techniques like UV-Vis, IR, NMR, ESI-MS, and single-crystal XRD. Complexes SC-1 and SC-3 exhibited octahedral geometry irrespective of the metal center. The complexes were systematically explored for electrocatalytic oxygen reduction reaction (ORR) by immobilizing them on a glassy carbon electrode using Nafion. These complexes showed selective two-electron catalytic reduction of O2 to H2 O2 in which complex SC-2 showed the highest selectivity (≈90%) and complex SC-4 showed the highest onset potential (0.75 V).

Controlled reduction of activated primary and secondary amides into aldehydes with diisobutylaluminum hydride.

A practical method is disclosed for the reduction of activated primary and secondary amides into aldehydes using diisobutylaluminum hydride (DIBAL-H) in toluene. A wide range of aryl and alkyl N-Boc, N,N-diBoc and N-tosyl amides were converted into the corresponding aldehydes in good to excellent yields. Reduction susceptible functional groups such as nitro, cyano, alkene and alkyne groups were found to be stable. Broad substrate scope, functional group compatibility and quick conversions are the salient features of this methodology.

Diversification of α-ketoamides via transamidation reactions with alkyl and benzyl amines at room temperature.

A wide range of N-tosyl α-ketoamides underwent transamidation with various alkyl amines in the absence of a catalyst, base, or additive. On the other hand, transamidation in N-Boc α-ketoamides was achieved in the presence of Cs2CO3. The reactions proceeded at room temperature and provided good to excellent yields of transamidation products under the optimized conditions. Broad substrate scope, functional group tolerance and quick conversions are the important features of the developed methodology.

Development of Routes for the Stereoselective Preparation of ß-Aryl-C-glycosides via C-1 Aryl Enones.

A wide range of enones derived from d-glucal, d-galactal, l-rhamnal, d-rhamnal, and l-arabinal underwent Heck-coupling with various arylboronic acids bearing electron-donating and -withdrawing groups in the presence of palladium acetate and 1,10-phenanthroline. These reactions provided synthetically useful C-1 aryl enones in good yields. Many sensitive functional groups as well as protecting groups present in arylboronic acids and enones, respectively, remained intact under optimized conditions. The stereoselective hydrogenation of C-1 aryl enones with Pd-C/H2 provides the ß-isomer of 2-deoxy-aryl-C-glycosides in excellent yield. The C-1 aryl enones were also used as precursors for the synthesis of 2-hydroxy-ß-aryl-C-glycosides. Regioselective C-2 halogenations and vinylations of C-1 aryl enones were achieved in excellent yields.

Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions.

Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,ß-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.

Regioselective Nitration of N-Alkyl Anilines using tert-Butyl Nitrite under Mild Condition.

Regioselective ring nitration of N-alkyl anilines is reported using tert-butyl nitrite. The reactions proceed efficiently with a wide range of substrates providing synthetically useful N-nitroso N-alkyl nitroanilines in excellent yields which can be easily converted into N-alkyl phenylenediamines and N-alkyl nitroanilines using Zn-AcOH and HCl/MeOH, respectively.

tert-Butyl nitrite mediated nitrogen transfer reactions: synthesis of benzotriazoles and azides at room temperature.

A conversion of o-phenylenediamines into benzotriazoles was achieved at room temperature using tert-butyl nitrite. The optimized conditions are also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides. This protocol does not require any catalyst or acidic medium. The desired products were obtained in excellent yields in a short span of time.

Copper promoted N-alkylation of sulfoximines with alkylboronic acid under mild conditions.

The copper meditated N-methylation of sulfoximines using methylboronic acid is reported. The reactions provide excellent yields in a short span of time under mild conditions. The optimized conditions were also found to be suitable for the N-alkylation of sulfoximine with different alkylboronic acids. In addition, N-methylation and cyclopropylation of the bioactive l-methionine sulfoximine derivative was demonstrated under standard reaction conditions.

Mononuclear [(BP)(2)MX](n+) (M = Cu(2+), Co(2+), Zn(2+); X = OH(2), Cl(-)) complexes with a new biphenyl appended N-bidentate ligand: structural, spectroscopic, solution equilibrium and ligand dynamic studies.

A new series of five-coordinate [(BP)2MX]n+ complexes, (where X = OH2, M = Zn(II) (1), Cu(II) (2); X = Cl-, M = Cu(II) (3), Co(II) (4)) with a new bidentate chelating ligand [{N,N(1,1'-biphenyl-2,2'-dimethylene)-N(2-pyridyl methyl)} amine] with a biphenyl group (BP), have been synthesized and characterized by X-ray crystal structure and combined spectroscopic methods. They display unique trigonal bipyramidal (TBP) geometry, influenced by the bidentate ligand. The Zn(II) complex 1 reveals ligand dynamics due to an atropisomeric biphenyl moiety as indicated by variable temperature (VT) proton NMR spectroscopy. The calculated free energy for the inversion of the bridged biphenyl is approximately 13.08 kcal mol-1 (Tc = 273 K, Delta(nu) = 82.8 Hz, J = 8.7 Hz). The absorption spectra of Cu(II) complexes 2 and 3, in CH2Cl2 display greatly enhanced d-d bands (800-950 nm, epsilon>500 M-1 cm-1). On the other hand, complex 2 in N,N-dimethylformamide (DMF) showed almost 50% reduction in absorption intensity as DMF, a coordinating solvent, displaces the weakly-coordinated tertiary amine-nitrogens of the ligand and this competitive binding was studied by electronic absorption spectroscopy. When the mononuclear copper aqua complex 2 was treated with a base, a dicopper dihydroxide complex, [{(BP)Cu}2(mu-OH)2]2+, (2a) was obtained. The same phenomenon was also observed with chloro complex 3 when treated with a base. This mono-dicopper equilibrium and conversion of 2 --> 2a was monitored by UV-vis spectroscopy. Copper(II) complexes 2 and 3 displayed reverse EPR spectra consistent with the TBP geometry. Cyclic voltammetry of 2 and 3 in DMF showed an irreversible redox wave owing to Cu(II)/Cu(I) of five and four-coordinate species. The solution magnetic moment values of 1.76, 1.81 and 4.47 microB for 2, 3 and 4, respectively, are in agreement with Cu(II) (S = 1/2) and Co(II) (S = 3/2) high-spin configurations. The 1H NMR of 4 displays sharp but hyperfine shifted signals for the ligand protons between -30 to +220 ppm. The ESI-mass data complement the data obtained from X-ray structure.

First hexanuclear copper(II) pyrophosphate through hydrolysis of phosphodiester with a dicopper complex.

Facile hydrolysis of a phosphodiester promoted by a dicopper bis(mu-hydroxo) complex containing a new biphenyl appended N-bidentate ligand led to the isolation of the first example of hexameric copper pyrophosphate through 'in situ self assembly'.