Hisatoshi Konishi

Hydroformylation of olefins with paraformaldehyde catalyzed by rhodium complexes

The addition of formaldehyde to olefins is efficiently catalyzed by RhH2(O2COH)[P(i-Pr)3]2 and gives the corresponding aldehydes in neutral solution.

Carbonylation of benzyl chloride catalyzed by watersoluble palladium phosphine complex in a two-phase system

Abstract Benzyl chloride is carbonylated by water-soluble PdCl 2 [Ph 2 P( m -C 6 H 4 -SO 3 Na)] 2 in an aqueous NaOH/n-heptane, benzene, or anisole two-phase system to afford phenylacetic acid in 89–93% yields. Aqueous NaOH/n-BuOH system gives both phenylacetic acid and benzyl n-butyl ether in comparable yields. The reaction proceeds under atmospheric pressure of carbon monoxide at 50 °C. When the system is placed under CO atmosphere, carbon monoxide is absorbed immediately.

One-pot synthesis of naphtho[2,3-b]furan-4,9-diones by sequential coupling/ring closure reactions

Abstract Treatment of 3-phenyliodonio-1,2,4-trioxo-1,2,3,4-tetrahydronaphthalenides with terminal acetylenes in the presence of a bis(triphenylphosphine)palladium chloride-cuprous iodide catalyst or cuprous oxide in N -methylpiperidine or pyridine, respectively, furnished the corresponding 2-substituted naphtho[2,3- b ]furan-4,9-diones in moderate to good yields. The utility of this method was demonstrated in the synthesis of a cytotoxic natural product, 2-(1-hydroxyethyl)naphtho[2,3- b ]furan-4,9-dione.

Synthesis and properties of crown ether-modified phosphines and their use as ligands in transition metal catalysts

Abstract A novel series of crown ether-modified triarylphosphines, 1,2-diphenylphosphino-2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetraoxacyclodecin (IIIa) and its higher homolog (III) (common nomenclature is 3 n -diphenylphosphinobenzo-[3 n -crown- n ]ethers ( n = 4, 5, 6, and 7)), is reported. The thermodynamic parameters for the extraction of alkali metal picrates are evaluated. Phosphines III ( n = 5 and 6) form 1 : 1 stoichiometric crown-type complexes with na + and K + . The observed extractability is in good agreement with the cavity size selectivity concept. The thermodynamic parameters Δ H ° and T Δ S ° for the extractive complexation at dgC are −63 to −58 kJ/mol and −41 to −35 kJ/mol, respectively, thus Δ G ° is governed by the enthalpy term. These phosphines are applied to reactions in liquid-liquid or liquid-solid phases, as the auxiliary ligands of homogeneous palladium and rhodium catalysis. The catalytic activities correlated well with the extractabilities of the phosphine ligands. The compound [RhCl(cod)] 2 , combined with IIIc and IIId, shows high activities toward catalytic hydrogenation of potassium and caesium cinnamates, respectively. Replacement of allyl bromide with powdered sodium or potassium iodide in benzene to give allyl iodide are catalyzed by (τ-C 3 H 5 PdCl) 2 in the presence of phosphines III.

Synthesis of 3-methoxyquinolines via cyclization of 1-isocyano-2-(2-lithio-2-methoxyethenyl)benzenes

Abstract 2-(2-Isocyanophenyl)acetaldehyde dimethyl acetals were treated with excess LDA to generate 1-isocyano-2-(2-lithio-2-methoxyethenyl)benzenes, which cyclized intramolecularly to afford 3-methoxyquinolines in good to excellent yields.

The acid-catalyzed condensation of 2-propylresorcinol with formaldehyde diethyl acetal. The formation and isomerization of calix[4]resorcinarene, calix[5]resorcinarene, and calix[6]resorcinarene

Abstract The title reaction initially produced a mixture of three cyclic oligomers, calix[n]resorcinarenes (n= 4, 5, 6), as the major products. Under the conditions of their formation, the pentamer rapidly isomerized to the tetramer and the hexamer, while the hexamer slowly isomerized to the tetramer. A new cyclic oligomer, calix[5]resorcinarene, was isolated and characterized.

Meerwein-Ponndorf-Verley reduction of ketones and aldehydes catalyzed by lanthanide tri-2-propoxides.

Lanthanide tri-2-propoxides, Ln(i-PrO)3 (Ln=Nd, Eu, Gd, Dy, Er, Tm, Yb), are very efficient for the catalytic Meerwein-Ponndorf-Verley reduction. The catalytic activity of Gd(i-PrO)3 is about 103 times as high as that of Al(i-PrO)3. Compared with Gd(i-PrO)3, Yb(i-PrO)3 is less active for the reduction of ketones but is efficient for that of aldehydes.

Convenient synthesis of furopyranopyrandione derivatives by the can-mediated furan ring formation

4H,9H-Furo[3,2-c]pyrano[3,4-e]pyran-4,9-dione (8) and (10) and 4H,5H-furo[2,3-b]pyrano[3,4-e]pyran-4,5-dione derivatives (9) were prepared in one step by treating 4-hydroxy-2H,5H-pyrano[4,3-b]pyran-2,5-diones (6) and alkenes (7) (or phenylacetylene) in acetonitrile with 2 equivalents of cerium(IV) ammonium nitrate (CAN).

Production of 3-hydroxybutyric acid trimer by Bacillus megaterium B-124

Abstract Newly isolated Bacillus megaterium B-124, which accumulated poly(3-hydroxybutyric acid) (PHB) amounting to about 20% of its dry cell weight, was found to secrete 3-hydroxybutyric acid and its trimer into the culture broth. The culture conditions were investigated and it was found that optimum conditions gave 7.6 g of the trimer per liter in 3 d of culture under the optimum conditions. The changes in the amounts of PHB, 3-hydroxybutyric acid, and its trimer during culture did not simply show that the trimer was the direct product of intracellular degradation of PHB.

High-Performance Solution-Processed n-Channel Organic Thin-Film Transistors Based on a Long Chain Alkyl-Substituted C60 Derivative

We report on high-performance solution-processed n-channel organic thin-film transistors based on a long-chain alkyl-substituted fullerene derivative, C60-fused N-methylpyrrolidine-meta-dodecyl phenyl (C60MC12), by surface modification of an insulator. C60MC12 films were fabricated on self-assembled monolayer (SAM)-treated gate insulators by spin-coating, which was facilitated by hydrophilic patterning of the edge of the substrate. X-ray diffraction revealed that the crystallinity of C60MC12 films was improved by SAM treatment. The octadecyltrichlorosilane-treated device demonstrated a high mobility of 0.4–0.5 cm2 V-1 s-1, which is comparable with those of amorphous silicon thin-film transistors. An improvement in bias stress stability by the SAM treatment was also observed.