The occurrence of variable stoichiometry cocrystals offers the prospect to acquire more solid forms of the same system. The control of stoichiometry is extremely important concerning the purity and intellectual...

Oxidative cleavage of styrene CC double bond is accomplished by employing a nitrogen-rich triazine-based microporous organic polymer as an organocatalyst. We report this regioselective reaction as first of its kind with no metal add-ons to afford benzaldehydes up to 92% selectivity via an unusual Wackertype CC bond cleavage. Such a reaction pathway is generally observed in the presence of a metal catalyst. This polymer further shows high catalytic efficiency in an anaerobic oxidation reaction of benzyl alcohols into benzaldehydes. The reaction is mediated by a base via the in situ generation of hydride ions. This study is supported by experiments and computational analyses for a freeradical transformation reaction of oxidative CC bond cleavage of styrenes and a hydride elimination mechanism for the anaerobic oxidation reaction. Essentially, the study unveils protruding applications of metal-free nitrogen-rich porous polymers in organic transformation reactions.

Unlike traditional catalysts, a Cu(II) catalyst incorporated onto a new pyridine based porous organic polymer linked by carboxamide functionality has been developed by impregnation method. Materials are characterized using FT-IR, solid-state NMR, PXRD, SEM, TEM techniques. The uniform confinement effect of the Cu(II) loaded polymer is assured by energydispersive X-ray (EDX) elemental mapping, ICP and AAS spectroscopic analysis. The Cu(II) loaded material further employed as a heterogeneous catalyst for nitroarene reduction and reported as an excellent catalyst with improved performances over those reported using expensive and precious metals (like Au and Pd) on immobilized organic porous materials. The oxidation state of Cu in the catalytic cycle is corroborated with XPS analysis. The present study also emphasizes the role of pelectron rich organic porous polymer as promoter of electronic stature of finely dispersed Cu sites accountable for the excellent catalytic activity towards nitroarene reduction.

Herein, we report a general method for copper-catalyzed N-arylation of isatoic anhydrides with unsymmetrical iodonium salts at room temperature. The developed catalytic protocol is mild and operationally simple, and aryl(TMP)iodonium trifluoroacetate is employed as the arylating partner. The methodology offers the broad applicability of both structurally and electronically diverse aryl groups from aryl(TMP)iodonium salts to access N-arylated isatoic anhydrides in moderate to excellent yields (53–92%). Moreover, the substituted isatoic anhydrides are equally compatible with the protocol too. To demonstrate the synthetic utilities of the N-arylation process, we also report an alternative approach for biologically relevant fenamic acid derivatives and N,N′-diarylindazol-3-ones in a one-pot step economical system. In addition, the scale-up synthesis of flufenamic acid is also illustrated.

The subsistence of dissimilar stoichiometry in cocrystals offers more solid forms with varied therapeutic advantages. Crystallization is a delicate process, and even an insignificant deviation in the process can impact the overall product performance. The significance of seasonal environmental variables in designing such different stoichiometric cocrystals is assessed by nucleating at least six different cocrystals from phenazine and protocatechuic acid. The cocrystals were isolated under continuously changing seasonal environmental variables in a time window of two comprehensive calendar years. The results are concurrent with the imitated in vitro laboratory crystallization conditions and are demonstrated. Competitive slurry and mechanochemical grinding experiments are employed to probe the phase relationships between these cocrystal phases.