A Combined Experimental and Computational Study on the Cycloisomerization of 2‐Ethynylbiaryls Catalyzed by Dicationic Arene Ruthenium Complexes

Ruthenium‐catalyzed cycloisomerization of 2‐ethynylbiaryls was investigated to identify an optimal ruthenium catalyst system. A combination of [η⁶‐(p‐cymene)RuCl₂(PR₃)] and two equivalents of AgPF₆ effectively converted 2‐ethynylbiphenyls into phenanthrenes in chlorobenzene at 120 °C over 20 h. Moreover, 2‐ethynylheterobiaryls were found to be favorable substrates for this ruthenium catalysis, thus achieving the cycloisomerization of previously unused heterocyclic substrates. Moreover, several control experiments and DFT calculations of model complexes were performed to propose a plausible reaction mechanism.     

Asymmetric Synthesis of Indoline from Achiral Phthalimide Involving Crystallization-Induced Deracemization

Asymmetric synthesis was performed by combining the photochemical reaction of an achiral substrate followed by crystallization-induced deracemization. The results indicated that a fused indoline produced by photochemical intramolecular δ-hydrogen abstraction and cyclization of N-(5-chloro-2-methylphenyl)phthalimide crystallized as a racemic conglomerate. Since this substrate has an aminal skeleton, racemization involving a ring-opening and ring-closing equilibrium process occurred under suitable conditions. Efficient racemization was observed in acetone containing a catalytic base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Crystallization-induced dynamic deracemization by Viedma ripening from racemic indoline was performed with an excellent enantioselectivity of 99 % ee. Furthermore, one-pot asymmetric synthesis of the indoline was achieved by the photochemical reaction of achiral phthalimide followed by continuous attrition-enhanced deracemization converging to 99 % ee of enantiomeric crystals. This is the first example of asymmetric expression and amplification by photochemical hydrogen abstraction and crystallization-induced dynamic deracemization.     

Phospholipid-Modified ODS Monolithic Column for Affinity Prediction of Hydrophobic Basic Drugs to Phospholipids

A phospholipid-modified octadecyl silica (ODS) monolithic column was prepared and its interaction with basic hydrophobic drugs was studied. These drugs are of interest in pharmaceutical research because of their strong interaction with biomembranes. The amount of dimyristoylphosphatidylcholine trapped on the ODS surface was reproducible, and the results of the trinitrobenzenesulfonic acid assay suggested the formation of a monolayer on the surface. Both hydrophobic and electrostatic interactions acted between the model drugs and the phosphatidylcholine. The column was stable for 10 days at least. The column was applied to the affinity screening of basic drugs to phospholipid. Good correlation was obtained between log k and log P for the basic drugs lidocaine, quinidine, propranolol, imipramine, and chlorpromazine. The monolithic silica column allowed highly hydrophobic basic drugs such as imipramine and chlorpromazine to be assayed; these are difficult to analyze by using a conventional particle-packed column. These drugs were clearly separated from acidic drugs naproxen and warfarin on the log k versus log P plots. The thermodynamic studies revealed that the retention of the drug was an enthalpy-driven process, and that the decrease in enthalpy for the phospholipid-modified ODS monolithic column was larger than those for immobilized artificial membrane columns. Our results suggest that the phospholipid-modified ODS monolithic column is applicable to affinity screening of drugs to phospholipids.     

Mesomorphic behavior of new benzothiazole liquid crystals having Schiff base linker and terminal methyl group

正A homologous series of heterocycles,6-methyl-2-(4-alkoxybenzylidenamino)benzothiazoles,were synthesized and characterized using FT-IR,~1H and ~(13)C NMR and mass spectrometric analysis.Enantiotropic nematic phase was observed for shorter members.Smectic A phase only emerged from octyloxy derivative onwards.The terminal methyl group at the benzothiazole fragment and the Schiff base linkage influenced the mesomorphic behavior of the present series.     

Synthesis of Triarylpyridines in Thiopeptide Antibiotics by Using a C−H Arylation/Ring‐Transformation Strategy

We have described a C?H arylation/ring‐transformation strategy for the synthesis of triarylpyridines, which form the core structure of thiopeptide antibiotics. This synthetic method readily gave 2,3,6‐triarylpyridines in a regioselective manner by a two‐phase approach: C?H arylation (a nickel‐catalyzed decarbonylative Suzuki–Miyaura cross‐coupling and decarbonylative C?H coupling for the synthesis of 2,4‐diaryloxazoles) and ring transformation ([4+2] cycloaddition of 2,4‐diaryloxazoles with (hetero)arylacrylic acids). To showcase these methods, we have accomplished the formal synthesis of thiopeptide antibiotics GE2270 s and amythiamicins.     

Solute-solvent intermolecular vibronic coupling as manifested by the molecular near-field effect in resonance hyper-Raman scattering

Vibronic coupling within the excited electronic manifold of the solute all-trans-β-carotene through the vibrational motions of the solvent cyclohexane is shown to manifest as the "molecular near-field effect," in which the solvent hyper-Raman bands are subject to marked intensity enhancements under the presence of all-trans-β-carotene. The resonance hyper-Raman excitation profiles of the enhanced solvent bands exhibit similar peaks to those of the solute bands in the wavenumber region of 21,700-25,000 cm(-1) (10,850-12,500 cm(-1) in the hyper-Raman exciting wavenumber), where the solute all-trans-β-carotene shows a strong absorption assigned to the 1A(g) → 1B(u) transition. This fact indicates that the solvent hyper-Raman bands gain their intensities through resonances with the electronic states of the solute. The observed excitation profiles are quantitatively analyzed and are successfully accounted for by an extended vibronic theory of resonance hyper-Raman scattering that incorporates the vibronic coupling within the excited electronic manifold of all-trans-β-carotene through the vibrational motions of cyclohexane. It is shown that the major resonance arises from the B-term (vibronic) coupling between the first excited vibrational level (v = 1) of the 1B(u) state and the ground vibrational level (v = 0) of a nearby A(g) state through ungerade vibrational modes of both the solute and the solvent molecules. The inversion symmetry of the solute all-trans-β-carotene is preserved, suggesting the weak perturbative nature of the solute-solvent interaction in the molecular near-field effect. The present study introduces a new concept, "intermolecular vibronic coupling," which may provide an experimentally accessible∕theoretically tractable model for understanding weak solute-solvent interactions in liquid.     

Switching of Redox Properties Triggered by a Thermal Equilibrium between Closed‐Shell Folded and Open‐Shell Twisted Species

Thermally switchable redox properties have been reported to be due to a change in the spin state of newly designed overcrowded ethylenes, which can adopt closed‐shell folded and open‐shell twisted forms. In this study, tetrathienylanthraquinodimethane derivatives were designed to be in thermal equilibrium between a more stable folded form and less stable but more donating twisted diradical in solution, so that the oxidation potential can be controlled by heating/cooling. This is the first example of a switching of redox properties based on a thermally equilibrated twisted diradical, which can be more readily oxidized to the twisted dication.