Carbon–carbon/carbon–heteroatom bond formation via oxidative transformations is a heavily explored topic at the frontier of chemistry. Potassium persulfate (K2S2O8) has emerged as a cost-effective, suitable inorganic oxidant for a wide array of oxidative transformations, ranging from laboratory experiments to industrial processes. The current review provides a comprehensive coverage of oxidative transformations aided with K2S2O8 in the presence or absence of a transition-metal catalyst, critical assessment of the results, and underlying mechanisms. Organic chemists may find this review to be a useful guide for the expedient synthesis of new chemical entities, to formulate mechanistic manifolds involving the sulfate radical anion, or to design novel oxidative transformations. A detailed understanding of the unsolved mechanisms could further enrich the field.

The present study aims to investigate the molecular basis of water sorption behavior of rivaroxaban-malonic acid cocrystal (RIV-MAL). It was hypothesized, that the amount of water sorbed by a crystalline solid is governed by the surface molecular environment of different crystal facets and their relative abundance to crystal surface. Water sorption behavior was measured using a dynamic vapor sorption analyzer. The surface molecular environment of different crystal facets and their relative contribution were determined using single crystal structure evaluation and face indexation analysis, respectively. The surface area-normalized water sorption for rivaroxaban (RIV), malonic acid (MAL), and RIV-MAL at 90% RH/25 °C was 0.28, 92.6, and 11.1% w/w, respectively. The crystal surface of MAL had a larger contribution (58.7%) of hydrophilic (Hphi) functional groups and showed the “highest” water sorption (92.6% w/w). On the contrary, RIV had a larger surface contribution (65.2%) of hydrophobic (Hpho) functional groups, and the smaller contribution (34.8%) of Hphi+Hpho groups exhibited the “lowest” water sorption (0.28% w/w). The “intermediate” water sorption (11.1% w/w) by RIV-MAL, as compared to RIV, was ascribed to the increased surface contribution of Hphi+Hpho groups (from 34.8 to 42.1%) and reduced hydrophobic surface contribution (from 65.2 to 57.9%). However, the significantly higher water gained (∼39-fold) by the cocrystal as compared to RIV, despite the nominal change in the surface contributions, was further attributed to the relatively stronger hydrogen bonding interactions between the surface-exposed carboxyl groups and water molecules. The study highlights that the amount of water sorbed by the cocrystal is governed by the surface molecular environment and additionally by the strength of hydrogen bonding. This investigation has implications on designing materials with a desired moisture-sorption property.

Despite its synthetic potential, intramolecular acylation by the Minisci reaction remains unexplored. The development of a new intramolecular Minisci acylation under silver-free neutral conditions providing access to azafluorenones and fluorenones is described. Distinct from the current literature known approaches for Minisci acylation, the report described herein features a method that: (a) avoids the use of silver that is invariably used in Minisci acylation, (b) does not require any acidic conditions for the activation of pyridines, and

A hydrazone-based N′1,N′3-bis((E)-4-(diethylamino)-2–hydroxybenzylidene)isophthalohydrazide (NDHIPH), has been synthesized, characterized, and assessed for its highly selective and sensitive (limit of detection, 2.53 nM) response toward Al(III) via fluorescence enhancement in 95% aqueous medium. All experimental results of analytical studies are in good consonance with the theoretical studies performed. Further, this NDHIPH-Al(III) ensemble is used for selective and sensitive (12.15 nM) detection of explosive picric acid (PA) via fluorescence quenching. This reversible behavior of NDHIPH toward Al(III) and PA is used for the creation of a molecular logic gate.

Discussed herein is an unprecedented Ru-catalyzed one-pot unsymmetrical C-H difunctionalization of arenes comprising intramolecular hydroarylation of olefins and intermolecular annulation of alkynes. This unprecedented 2-fold C-H functionalization is validated on the basis of experimental and density functional theory (DFT) study. The transformation readily occurs with the assistance of methylphenyl sulfoximine (MPS) directing group in the presence of Ru catalyst forming two C-C and one C-N bonds in a single operation. The overall process is atom economical and step-efficient and provides unusual dihydrofuran-fused isoquinolone heterocycles. Further annulation of NH and the proximal o-C-H-arene of isoquinolone with alkynes build highly conjugated novel polycyclic compounds. Overall, three independent annulations in arene motifs are visualized and thoughtfully executed; finally, 5 ring-fused structural entities are constructed forming three C-C and two C-N bonds.

Metal-free insertion of a methylene group was achieved for the construction of a new C(sp 2 )−C(sp 3 )-H−C(sp 2 ) bond in order to prepare novel bis-heterocyclic scaffolds. The complete mechanistic investigations included experimental study and DFT calculations, and various symmetric and unsymmetric bispyrazoles as well as other pyrazole-based bis-heterocyclic molecules were prepared in moderate to high yields. Further modification of the bridged methylene group in the unsymmetric pyrazoles generated a chiral center to extend the scope of this method.

A one-pot synthesis of 2-aryl-3-alkyl/aryl-sulfonyl-(NH)-pyrroles from N-sulfonylpyrroles, developed for the first time, via palladium-catalyzed oxidative C-2 arylation followed by sulfonyl migration is described.

Thiazetidin-2-ylidenes have been designed as four membered N-heterocyclic carbenes (NHCs) using quantum chemical studies. These species are smaller analogs of thiazol-2-ylidenes, possess high singlet stability (57 kcal/mol) and large nucleophilicity...