Palash Pandit

FeCl3⋅6H2O-catalyzed intermolecular-cascade cyclization of acetoacetanilide: aldehyde-tuned synthesis to valuable 2-pyridone analogues.

The first ever breakthrough toward activation of β-ketoacetanilide and subsequent C-C and C-N bond-forming intermolecular-cascade cyclization processes is demonstrated by development of the unprecedented Lewis acid property of non-toxic FeCl(3)⋅6H(2)O. Aromatic, aliphatic, α,β-unsaturated, chiral sugar-based and chromone aldehydes were regio- and stereoselectively cyclized with acetoacetanilides toward construction of valuable N-containing highly functionalized 2-pyridones (see scheme for an example).

CeCl3·7H2O Catalyzed C–C and C–N Bond-Forming Cascade Cyclization with Subsequent Side-Chain Functionalization and Rearrangement: A Domino Approach to Pentasubstituted Pyrrole Analogues

CeCl(3)·7H(2)O is found as an efficient catalyst for new intermolecular domino reactions of three-, four- and seven-component assemblies of common precursors under benign reaction conditions. Generation of enaminioesters from β-keto esters and primary amines, activation of their allylic sp(3) C-H, vinylic sp(2) C-H and N-H bonds, multi C-C and C-N bond-forming cascade cyclization with 1,2-diketones and subsequent side-chain alkylation have been developed to construct functionalized pentasubstituted pyrroles and their chiral analogues. The scope of the domino reaction is successfully explored toward synthesis of highly aryl-substituted pyrroles, pentasubstituted pyrroles bearing C2-olefinic side-chain and spiro-2-pyrrolinones and their chiral analogues via unusual side-chain amination, elimination and ring contraction. The new domino reaction is operationally simple, robust, substrate specific, selective and high yielding.

PhIO as a powerful cyclizing reagent: regiospecific [3+2]-tandem oxidative cyclization of imine toward cofacially self-aggregated low molecular mass organic materials.

The powerful cyclization and tandem oxidation property of environmentally benign PhIO is developed for the first time, which leads to regiospecific [3+2]-tandem oxidative cyclization of imine at room temperature in rapid access to a new class of compounds, 1,2-functionalized 4,5-diarylimidazoles, in excellent yield with synthetic efficiency. Size, shape, and activity of the involved nanoreactors for the green approach built up from various surfactants are investigated. Spontaneous generation of low molecular mass self-aggregated organic materials, their cofacial one-dimensional packing, and interesting photophysical properties are reported.

Non-Planar [n]Cyclo-1,8-carbazolylenes (n=3,4,6) and [3]Cyclo-1,8-carbazolylenyl B, P, PO, SiPh Complexes

A new family of non-planar heterocyclic molecules consisting of carbazoles was created. A bowl-shaped cyclodimer, a flake-shaped cyclotrimer, a double-decker-ring-shaped cyclotetramer and a cyclohexamer were synthesized by Ni0 -mediated one-shot cyclo-oligomerization of 1,8-dibromocarbazole, and were named [n]cyclo-1,8-carbazolylenes (n=3,4,6). [3]Cyclo-1,8-carbazolylene was found to act as a trivalent tridentate ligand for heteroatoms (B, P, Si), giving flake-shaped complexes. The boron derivative acted as a Lewis acid, and the tetra-coordinated complexes showed an unprecedented red-shift of absorption and emission spectra by the coordination. The synthetic method, the distorted C2 or C1 symmetric shape, the trivalent tridentate coordination ability and the kinds of introduced heteroatoms of [3]cyclo-1,8-carbazolylenes, the electronic structure, the photophysical property, and the Lewis acidity were distinct from those of related subporphyrins/subphthalocyanines.

Application of Hydrazine-Embedded Heterocyclic Compounds to High Voltage Rechargeable Lithium Organic Batteries

Hydrazine-embedded heterocyclic compounds with dimeric dimethylacridine (1b), carbazole (2b), and phenothiazine (3b) skeletons were applied to cathode active materials of rechargeable lithium organic batteries, and the performance of the batteries was evaluated. The charge/discharge curves exhibited clear plateaus in the high voltage range of 3.3–3.7 V. The capacities of the plateau regions were comparable to the calculated capacities corresponding to the one-electron redox of the molecules. The amount of the active compound 3b could be increased up to 30 wt% in the electrode composite, and fast charge/discharge performance was also observed.