Urea-Promoted Neat Synthesis of Fused Dihydroisoquinolines and Disubstituted Pyridines: A Mechanistic Observation with Molecular-Sensing Studies.

An efficient and short synthesis of fused dihydroisoquinolines, diaryl substituted pyridine derivatives in good to high yields has been established by using an environmentally safe, solvent-metal-oxidant-free tandem approach. In this article, we discuss how the electrocyclic reaction is more pronounced in the solid phase in the presence of urea, whereas the typical aza-Michael addition is more prominent in presence of arylamine in the solution phase for 3-(2-formylcycloalkenyl)acrylic ester derivative substrates. The wide range of substrates and urea-promoted neat synthesis made our approach more significant in medical and also analytical science. Moreover, an isoquinoline alkaloid decumbenine B analogue has been synthesized by using our newly developed neat methodology. We have also investigated the photophysical properties of the synthesized fused dihydroisoquinoline derivatives. One of the synthesized molecules was used as a sensor for the selective detection of toxic picric acid. Therefore, the effective neat synthesis and molecular sensing applications of these compounds made our approach more exciting in the field of heterocyclic chemistry.

Synthesis of Multifused Pyrrolo[1,2-a]quinoline Systems by Tandem Aza-Michael-Aldol Reactions and Their Application to Molecular Sensing Studies.

Herein, we have presented a weak acid-promoted tandem aza-Michael-aldol strategy for the synthesis of diversely fused pyrrolo[1,2-a]quinoline (tricyclic to pentacyclic scaffolds) by the construction of both pyrrole and quinoline ring in one pot. The described protocol fabricated two C-N bonds and one C-C bond in the pyrrole-quinoline rings which have been sequentially formed under transition-metal-free conditions by the extrusion of eco-friendly water molecules. A ketorolac drug analogue has been synthesized following the current protocol, and one of the synthesized tricyclic pyrrolo[1,2-a]quinoline fluorophores has been used to detect highly toxic picric acid via the fluorescence quenching effect.

Chemical synthesis of ß-D-ManNAc containing pentasaccharide repeating unit of the exopolysaccharide from Lactobacillus rhamnosus BIM B-1039 in the form of its p-methoxyphenyl glycoside.

Total synthesis of the pentasaccharide repeating unit of the exopolysaccharide from Lactobacillus rhamnosus BIM B-1039 is accomplished by bis-glycosylation on a suitably protected trisaccharide di-ol. The stereochemically challenging ß-D-ManNAc residue was introduced through a glucose derivative to ensure ß-selectivity followed by inversion of the 2-OH position with azido group to form the desired mannosamine moiety. The use of the p-methoxyphenyl glycoside at the reducing end was triggered by the fact that its oxidative cleavage followed by the formation of the trichloroacetimidate derivative will open up the scope for further conjugation of suitable aglycon.

Chemical synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from Ruminococcus gnavus.

Microorganisms present in the guts are the causative agents for various diseases in humans. More and more studies are correlating such diseases and the responsible microorganism. The Gram-positive bacterium Ruminococcus gnavus (R. gnavus) has been identified to be responsible for symptoms of Crohn's disease. R. gnavas produces a glucorhamnan polysaccharide and it is postulated that this polysaccharide induces inflammatory response through toll-like receptor 4 (TLR4). The current manuscript describes the chemical synthesis of the pentasaccharide repeating unit of the O-polysachharide from R. gnavus. The major challenge associated with this particular synthesis is the presence of two consecutive 1,2-cis glucose units. The target oligosaccharide is achieved through a linear strategy from commercially available sugars through rational protecting group manipulation. 1,2-cis glycosylation of glucose through remote participation of acyl group at the 6-O position is used successfully with excellent yield. In both cases, sole 1,2-cis products are obtained at -20 °C through the activation of thioglycosides.

Chemical synthesis of the rare D-Fuc3NAc containing tetrasaccharide repeating unit of the O-antigenic polysaccharide from E. coli O74.

Chemical synthesis of the tetrasaccharide repeating unit of the O-antigen from E. coli O74 is accomplished by a convergent [2 + 2] block synthesis strategy. The challenging rare D-Fuc3NAc has been prepared using DTBP and TIPST mediated deoxygenation reaction. Other monosaccharide synthons are prepared through rational protecting group manipulations and the stereoselective glycosylations are achieved either by the activation of thioglycoside or glycosyl trichloroacetimidate. The target tetrasaccharide is made in the form of its 2-aminoethyl glycoside to facilitate further glycoconjugate formation without affecting the anomeric stereochemistry.

One-pot tandem cyclisation to pyrrolo[1,2-a][1,4]benzodiazepines: a modified approach to the Pictet-Spengler reaction.

We have reported a one-pot two-step methodology for the synthesis of highly condensed heterocycles, pyrrolo[1,2-a][1,4]benzodiazepines, by a modified Pictet-Spengler reaction under mild conditions in a short time. Our approach has a few advantages over the conventional two components synthesis as it is step and atom economic, environmentally benign and a convergent synthetic method. We have discussed here the broad substrate scope of this novel methodology.

Surface-coupling of Cerenkov radiation from a modified metallic metamaterial slab via Brillouin-band folding.

Metallic metamaterials with positive dielectric responses are promising as an alternative to dielectrics for the generation of Cerenkov radiation [J.-K. So et al., Appl. Phys. Lett. 97(15), 151107 (2010)]. We propose here by theoretical analysis a mechanism to couple out Cerenkov radiation from the slab surfaces in the transverse direction. The proposed method based on Brillouin-zone folding is to periodically modify the thickness of the metamaterial slab in the axial direction. Moreover, the intensity of the surface-coupled radiation by this mechanism shows an order-of-magnitude enhancement compared to that of ordinary Smith-Purcell radiation.