Zinc-catalyzed N-Aroylation of Sulfoximines with Carboxylic Acids.

A zinc-mediated C(sp2)-N dehydrative cross-coupling between carboxylic acids and NH-sulfoximines to affords N-aroylated sulfoximines under mild reaction conditions is described. A wide variety of NH-sulfoximines were coupled with readily available carboxylic acids to provide the corresponding N-aroylated sulfoximines in good to excellent yields.

Palladium-catalyzed synthesis of 2,3-disubstituted indoles via arylation of ortho-alkynylanilines with arylsiloxanes.

In this study, we report the electrophilic cyclization of N,N-dimethyl-o-alkynylanilines with arylsiloxanes in the presence of [Pd(OAc)2] and Ag2O catalytic system, which leads to the efficient synthesis of indoles, similar to the one that is obtained through Larock indole synthesis. A range of aryl(trimethoxy)silanes with EDGs and EWGs were successfully utilized for the synthesis of a diverse variety of substituted indoles via the cleavage of the C-Si bond. This protocol exhibits good functional group tolerance and wide substrate scope to provide 2,3-diaryl-N-methylindoles in 26-88% yields.

Base-mediated chalcogenoaminative annulation of 2-alkynylanilines for direct access to 3-sulfenyl/selenyl-1H-indoles.

An efficient and transition metal-free synthesis of 3-sulfenyl/selenyl-1H-indoles via a base-assisted chalcogenoaminative annulation of 2-alkynyl aniline with disulfides/diselenides is described. A series of 2-alkynylanilines were found compatible with dichalcogenides in this transformation providing 3-sulfenyl/selenyl-1H-indoles in good to excellent yields. The presented methodology has the advantages of easily available raw materials, functional group tolerance, and a wide range of substrates that provide access to 3-sulfenylindoles and 3-selenylindoles.

Electrochemical Bisarylation of Carbonyls: A Direct Synthetic Strategy for Bis(indolyl)methane.

An interesting electrochemical direct bisarylation of carbonyls with indole derivatives to afford the corresponding bis(indolyl)methane (BIM) derivatives is described. The developed protocol is suitable for aliphatic, aromatic, and heteroaromatic aldehydes, which react with various electron-rich and electron-poor indoles to afford the corresponding BIMs in good to excellent yields. Isatin derivatives also underwent bisarylation with various indole derivatives under the influence of current to afford the corresponding BIMs in excellent yields.

Cesium carbonate-catalyzed synthesis of phosphorothioates via S-phosphination of thioketones.

A highly efficient and environmentally-friendly base-mediated transition metal-free direct thiophilic catalytic approach is reported for the synthesis of S-benzhydryl-phosphorothioates by reacting phosphite nucleophiles with diarylmethanethione. A wide variety of thioketones were coupled with different phosphite derivatives to provide the corresponding phosphorothioates in good to excellent yields. The control experiments and density functional theory (DFT) calculations rely on the regio-selective thiophilic addition of a phosphite nucleophile via umpolung protocols.

Blue LED-Mediated Syntheses of Arylazo Phosphine Oxides and Phosphonates via N-P Bond Formation.

The synthesis of (E)-diphenyl(aryldiazenyl)phosphine oxides and dialkyl (E)-(aryldiazenyl)phosphonates via visible light-mediated N-P bond formation between diazo species and phosphine oxides and phosphite derivatives, respectively, is described. The diazo species were generated via the reaction of aniline with isoamyl nitrite, which upon reaction with phosphorus surrogates generated arylazophosphine oxides and arylazo phosphonates in good to excellent yields. This sustainable chemical process offers a broad substrate scope and reasonably viable product formation.

Blue LED-Promoted Syntheses of Phosphorothioates and Phosphorodithioates.

An environmentally friendly and resourceful modular protocol for the synthesis of phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates under blue light-emitting diode irradiation is described. The blue LED-promoted P-S, P-Se, and P-Te bond constructions occurred under metal-free, ligand-free, oxidant-free, and photocatalyst-free conditions with minimum chemical waste generation and high atom economy providing the resulting phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates in good to excellent yields.

Highly atom-economical, catalyst-free, and solvent-free phosphorylation of chalcogenides.

Silica gel promoted, catalyst-free and solvent-free S-P, Se-P and Te-P bond formations are described. A variety of disulfides coupled with diarylphosphine oxides provide the corresponding phosphinothioates in excellent yields. For the first time, diselenides and ditellurides reacted with dialkyl phosphites under catalyst-free conditions to provide the corresponding phosphoroselenoates and phosphorotelluroates, respectively, in good to excellent yields.

Site-specific growth of oriented ZnO nanocrystal arrays.

We report on the growth of ZnO nanocrystals having a hexagonal, prismatic shape, sized 700 nm × 600 nm, on bare indium tin oxide (ITO) substrates. The growth is induced by a low ion flux and involves a low-temperature electrodeposition technique. Further, vertically aligned periodic nanocrystal (NC) growth is engineered at predefined positions on polymer-coated ITO substrates patterned with ordered pores. The vertical alignment of ZnO NCs along the c-axis is achieved via ion-by-ion nucleation-controlled growth for patterned pores of size ≈600 nm; however, many-coupled branched NCs with hexagonal shape are formed when a patterned pore size of ≈200 nm is used. X-ray diffraction data is in agreement with the observed morphology. A mechanism is proposed to interpret the observed site-specific oriented/branched growth that is correlated to the pore size. As ordered NC arrays have the potential to generate new collective properties different from single NCs, our first demonstration of a cost effective and facile fabrication process opens up new possibilities for devices with versatile functionalities.

Hypocalcemia in jaundiced neonates receiving phototherapy.

OBJECTIVE: To determine the frequency of hypocalcemia in term neonates with jaundice receiving phototherapy. METHODS: This was a cross sectional study conducted at Neonatal intensive care unit, National Institute of Child Health, Karachi from 1st January 2014 to 30th December 2014. A total of 123 term neonates with jaundice of either gender managed by phototherapy were enrolled in the study. Gestational age was assessed through modified Ballard scoring. Duration of phototherapy was recorded. A sample of 3 ml of blood was sent to the laboratory for serum calcium level before initiating phototherapy and after 24 hours of continued phototherapy. All the data were recorded in the preformed proforma. Data was analyzed using SPSS version 19. P value <0.05 was taken as significant. RESULTS: The mean age of the neonates was 8.35±6.74 days. Mean gestational age at the time of birth was 39.08±1.37 weeks. Mean duration of jaundice was 2.4±1.20 days. Mean duration of phototherapy was 1.74±0.98 days. Serum calcium level before and after 24 hours of initiating phototherapy was 8.73±0.68 mg/dl and 7.47±0.82mg/dl respectively Frequency of hypocalcemia in term jaundiced neonates receiving phototherapy were observed in 22.76% (28/123). CONCLUSIONS: The frequency of hypocalcemia is significant in the jaundiced neonates treated with phototherapy. One needs to be vigilant in dealing neonates in this context while serial monitoring for hypocalcemia and its complications should be considered in institutional policy and research priority.