Accessing C2-Functionalized 1,3-(Benz)azoles through Transition Metal-Catalyzed C−H Activation

The skeletal presence of 1,3-azoles in a variety of bioactive natural products, pharmacophores, and organic materials demands the derivatization of such heteroarenes regioselectively. Plenty of cross-coupling as well as cyclocondensation reactions have been performed to build up these skeletons but remained commercially unrealizable. A couple of severe drawbacks are faced by these traditional protocols that require a more straightforward strategy to obviate them. Transition metal-catalyzed C−H functionalization has emerged as a superior alternative in that context. 1,3-Azoles and their benzo counterparts have been extensively functionalized exploiting both noble and earth-abundant transition metals. Lately, C-2 functionalization have gained much traction due to the ease of attaining high regioselectivity and installation of synthetically manipulative functionalities. This critical review presents a bird‘s eye view of all major C-2 functionalization of (benz)azoles catalyzed by a diverse set of metals performed over the past 15 years.     

Dimensionality,nematicity and superconductivity in Fe-based systems

Study of Fe based compounds have drawn much attention due to the discovery of superconductivity as well as many other exotic electronic properties. Here, we review some of our works in these materials carried out employing density functional theory and angle resolved photoemission spectroscopy. The results presented here indicate that the dimensionality of the underlying electronic structure plays important role in deriving their interesting electronic properties. The nematicity found in most of these materials appears to be related to the magnetic long range order. We argue that the exoticity in the electronic properties are related to the subtlety in competing structural and magnetic instabilities present in these materials.     

Interconnectivity between Surface Reactivity and Self-Assembly of Kemp Elimination Catalyzing Nanorods

Understanding the fundamental facts behind dynamicity of catalytic processes has been a longstanding quest across disciplines. Herein, we report self-assembly of catalytically active gold nanorods that can be regulated by tuning its reactivity towards a proton transfer reaction at different pH. Unlike substrate-induced templating and co-operativity, the enhanced aggregation rate is due to alteration of catalytic surface charge only during reactivity as negatively charged transition state of reactant (5-nitrobenzisoxazole) is formed on positively charged nanorod while undergoing a concerted E2-pathway. Herein, enhanced diffusivity during catalytic processes might also act as an additional contributing factor. Furthermore, we have also shown that nanosized hydrophobic cavities of clustered nanorods can also efficiently accelerate the rate of an aromatic nucleophilic substitution reaction, which also demonstrates a catalytic phenomenon that can lead to cascading of other reactions where substrates and products of the starting reactions are not directly involved.     

Direct meta-C−H Perfluoroalkenylation of Arenes Enabled by a Cleavable Pyrimidine-Based Template

The development of efficient and mild methods for the synthesis of organofluorine compounds is of foremost interest in various fields of chemistry. A direct pyrimidine-based selective meta-C−H perfluoroalkenylation of arenes involving several commercially available perfluoroolefins is described. The synthetic versatility of the protocol is demonstrated by an extensive substrate scope including different benzylsulfonyl, alkylarene and phenylacetic acid scaffolds. The generality of this methodology including the meta-C−H perfluoroalkenylation of Ibuprofen, the facile cleavage of the directing group and gram-scale reactions are presented.     

Size distributions of aerosols in an indoor environment with engineered nanoparticle synthesis reactors operating under different scenarios

Size distributions of nanoparticles in the vicinity of synthesis reactors will provide guidelines for safe operation and protection of workers. Nanoparticle concentrations and size distributions were measured in a research academic laboratory environment with two different types of gas-phase synthesis reactors under a variety of operating conditions. The variation of total particle number concentration and size distribution at different distances from the reactor, off-design state of the fume hood, powder handling during recovery, and maintenance of reactors are established. Significant increases in number concentration were observed at all the locations during off-design conditions (i.e., failure of the exhaust system). Clearance of nanoparticles from the work environment was longer under off-design conditions (20 min) compared to that under normal hood operating conditions (4–6 min). While lower particle number concentrations are observed during operation of furnace aerosol reactors in comparison to flame aerosol reactors, the handling, processing, and maintenance operations result in elevated concentrations in the work area.