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.
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