Mild blue light-mediated N–H insertion of indole and its derivatives into aryldiazoesters has been reported in a batch and flow strategy to afford the corresponding N-alkylated product in moderate-to-excellent yield. Detailed high-performance liquid chromatography-based reaction kinetics measurements, control experiments, and kinetic isotope effect reveal that 3-substituted indoles with electron-withdrawing groups such as −CN and −CHO facilitated the product formation, whereas the electron-donating group retarded the process. The neutral indole performed in between them. Furthermore, Hammett plot and density functional theory-based transition-state optimization studies showed substantial correlation of the electronic nature of the substituents at the C3 position of indoles with the rate of the N–H insertion reaction. The strategy was utilized to synthesize a key intermediate for the natural product (−)-psychotrimine.

There are great efforts of synthesizing imidazolium-based ionic liquids (ILs) for developing new antibiotics as these molecules have shown strong antibacterial activities. Compared to a single-hydrocarbon-chained IL, the lipid analogues (LAs) with two chains are more effective. In the present study, the LA molecule MeIm­(COOH)Me(Oleylamine)­Iodide has been synthesized and its surface activities along with the effectiveness in restructuring of a model cellular membrane have been quantified. The molecule is found to be highly surface active as estimated from the area–pressure isotherm of a monolayer of the molecules formed at the air–water interface. The X-ray reflectivity (XRR) studies of a monolayer dip-coated on a hydrophilic substrate have shown the structural properties of the layer which resembles to those of unsaturated phospholipids. The LA molecules are observed to fluidize a phospholipid bilayer formed by the saturated lipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). At a lower surface pressure, the lipid monolayer of DPPC has exhibited a thickening effect at a low concentration of added LA and a thinning effect at higher concentration. However, at a high surface pressure of the monolayer, the thickness is found to decrease monotonically. The in-plane pressure-dependent interaction of LA molecules with model cellular membrane and the corresponding perturbation in the structure and physical properties of the membrane may be linked to the strong lysing effect of these types of molecules.

Here in we have reported a blue LED mediated reaction of aryl diazoacetate with stoichiometric 1, 4-dioxane/ tetrahydropyran (THP) and various heterocycles like indoles, pyrroles, phthalimide, thiazolidinedione and hydantoin in...

Organomercurials, such as methylmercury (MeHg ), are among the most toxic materials to humans. Apart from inhibiting proteins, MeHg exerts its cytotoxicity through strong binding with endogenous thiols cysteine (CysH) and glutathione (GSH) to form MeHgCys and MeHgSG complexes. Herein, it is reported that the N,N-disubstituted benzimidazole-based thione 1 containing a N-CH CH OH substituent converts MeHgCys and MeHgSG complexes to less toxic water-soluble HgS nanoparticles (NPs) and releases the corresponding free thiols CysH and GSH from MeHgCys and MeHgSG, respectively, in solution by unusual ligand-exchange reactions in phosphate buffer at 37 °C. However, the corresponding N-substituted benzimidazole-based thione 7 and N,N-disubstituted imidazole-based thione 3, in spite of containing a N-CH CH OH substituent, failed to convert MeHgX (X=Cys, and SG) to HgS NPs under identical reaction conditions, which suggests that not only the N-CH CH OH moiety but the benzimidazole ring and N,N-disubstitution in 1, which leads to the generation of a partial positive charge at the C2 atom of the benzimidazole ring in 1:1 MeHg-conjugated complex of 1, are crucial to convert MeHgX to HgS NPs under physiologically relevant conditions.

The direct C2-H oxidation and imination of a wide variety of azoles was achieved by using a commercially available simple K2CO3/I2 reagent combination. The iodinated azole adduct, produced via the in situ generation of N-heterocyclic carbene, is the key intermediate for C2-H oxidation, imination, and amination of azoles. Significantly, these reactions proceed under mild conditions with high to excellent yields, are scalable to large quantity and exhibit a broad substrate scope. Interestingly, this direct C2-H imination method allowed us to access various pharmacologically active N6-alkyl or N6-aryl substituted benzimidazoquinazolinone scaffolds through intramolecular C-H imination in a sequential one-pot reaction.