Synthesis of coumarins by Pt-catalyzed hydroarylation of propiolic acids with phenols

Synthesis of coumarins from phenols and propiolic acids was examined by using a Pt catalyst such as PtCl₂/AgOTf, K₂PtCl₄/AgOTf, and K₂PtCl₄/AgOAc. Propiolic acid reacted even with less reactive phenols in trifluoroacetic acid to give coumarins and dihydrocoumarins. In the case of substituted propiolic acids, phenylpropiolic acid and 2-octynoic acid, the reactions proceeded selectively to afford coumarins in good to high yields.     

Glycosyl azide—a novel substrate for enzymatic transglycosylations

Glycosyl azides are new efficient donors for glycosidases. Their high water solubility facilitates transglycosylations with comparable or better yields than common O-glycosides. The azido group totally changes the β-GalNAc-ase/β-GlcNAc-ase ratio in β-N-acetylhexosaminidases (from the usual 0.3-1.0 to <0.01), contrary to all known aglycons.     

Electrochemical characterization of poly(vinylidenefluoride)-zinc triflate gel polymer electrolyte and its application in solid-state zinc batteries

Gel polymer electrolyte (GPE) films comprising of poly(vinylidenefluoride), propylene carbonate, ethylene carbonate and zinc trifluoromethane sulfonate are prepared and characterized. The composition of GPE is optimized to contain minimum liquid components with a maximum specific conductivity of 3.94×10⁻³ S cm⁻¹ at (25±1) °C. A detailed investigation on the properties such as ionic conductivity, transport number, electrochemical stability window, reversibility of Zn/Zn²⁺ couple and Zn/gel electrolyte interfacial stability have been carried out. The ionic conductivity follows a VTF behaviour with an activation energy of about 0.0014 eV. Cationic transport number varies from 0.51 at 25 °C to 0.18 at 70 °C. Several cells have been assembled with GPE as the electrolyte, zinc as the anode, γ-MnO₂ as the cathode and their charge–discharge behaviour followed. Capacity values of 105, 82, 64 and 37 mAh/g of MnO₂ have been achieved at 10, 50, 100 and 200 μA/cm² discharge current densities, respectively. The discharge capacity values are almost constant for about 55 cycles for all values of current densities. Cyclic voltammetric study of MnO₂ electrode in Zn/GPE/MnO₂ cell clearly shows intercalation/deintercalation of Zn²⁺.     

Diversification of shotgun process

Three protocols for shotgun process are put forth in which simultaneous multi-fold reactions occur exclusively to each other. The first one involves simple combination of selective and non-selective reactions. Even if the simple protocol fails to give rise to the high selectivity, satisfactory outcome can be achieved by kinetic control or adjustment of functional groups.     

Sc(OTf)3-catalyzed alkylation of indoles with propargyl alcohols: an expeditious synthesis of 3-substituted indoles

Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity.     

Yb(OTf)3-catalyzed cyclization of an N-silylenamine with 2-methylene-1,3-cyclohexanedione to afford a 7,8-dihydroquinolin-5(6H)-one derivative and its application to the one-pot conversion to a 2,3,5-trisubstituted quinoline derivative

A catalytic amount of ytterbium triflate (Yb(OTf)₃) promotes the cyclization of an N-silylenamine with in situ generated 2-methylene-1,3-cyclohexanedione and 2-methylenecyclohexanone to produce the corresponding 2,3-disubstituted 7,8-dihydroquinolin-5-one and 5,6,7,8-tetrahydroquinolin-5-one in moderate to good yields. A one-pot conversion of 7,8-dihydroquinolin-5-one to the quinoline derivative also proceeded in good yield.     

Bismuth triflate catalyzed Claisen rearrangement of allyl naphthyl ethers

Bismuth triflate was found to be an efficient catalyst for the Claisen rearrangement of allyl naphthyl ethers. The reaction proceeds smoothly with a catalytic amount of bismuth triflate (20 mol %) to afford the corresponding ortho-allyl naphthol in moderate to good yields in most cases.     

Cyclic vinylogous triflate hemiacetals as new surrogates for alkynyl aldehydes

Cyclic vinylogous triflate hemiacetals can serve as ‘synthetic equivalents’ for alkynyl aldehydes: treatment of a vinylogous triflate hemiacetal with excess amounts of Grignard reagents produces acyclic alkynyl alcohols in good to high yields. This transformation likely involves the Grob-type C-C bond cleaving fragmentation to form the alkynyl aldehyde in situ. Subsequent nucleophilic attack of the Grignard reagent furnishes secondary alkynols. Vinylogous triflate hemiacetals are easily prepared by DIBALH reduction of vinylogous acyl triflates, which are derived from cyclic 1,3-diketones.     

The Purification of Glucose Type Glycosyl Nitrate and the Synthesis of Spacer—armed N—Acetyllactosamines and Their Dimers

Our previous paper1,2reported the results of selective synthesis of mannose type glycosides and their dimers in our attempt to synthesize derivatives of N-acetyllacto- samine, which could have potential activity of anti-metastasis3. Further studies on the glycosylation of the accepters exploiting glycosyl nitrate instead of the acetate as donor showed interesting chemoselectivity between the two kinds of donor, namely, the glucose type and the mannose type. The reactivity difference of the t…     

1,4‐Addition polymerization of 1,4‐bis(4‐benzylpyridinium)butadiyne triflate in a dipolar aprotic solvent

1,4‐Bis(4‐benzylpyridinium)butadiyne triflate was aggregated in dimethylformamide and spontaneously converted into the 1,4‐addition type of polydiacetylene. The polymerization took place in a dipolar aprotic solvent with a large dielectric constant that could enhance the aggregation of the ionic diacetylene salt through the electrostatic interaction. The molecular weight of the diacetylene was leveled off after 30 h at 80 °C to reach 1.5 × 10⁴ (number‐average molecular weight) that consisted of the 1,4‐addition type of polydiacetylene similar to polydiacetylenes obtained in the conventional solid‐state polymerization. Electron spin resonance spectra revealed that diradicals were generated at the earlier state aggregation to give rise to a solution polymerization. The UV spectra also suggested the presence of the activated aggregation associated with the polymerization as well as the eximer emission spectra. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3534–3541, 2002