C. Akira Horiuchi

A novel one-pot synthesis of 3-acetyl- and 3-benzoylisoxazole derivatives using ammonium cerium nitrate (CAN)

Abstract The reaction of dipolarophiles (several alkenes and alkynes) with ammonium cerium(IV) nitrate ((NH 4 ) 2 Ce(NO 3 ) 6 , CAN(IV)) in acetone under reflux gave 3-acetylisoxazole derivatives. In the case of acetophenone, 3-benzoylisoxazole derivatives were obtained. Moreover, it was found that yields of isoxazole derivatives were improved using ammonium cerium(III) nitrate tetrahydrate ((NH 4 ) 2 Ce(NO 3 ) 5 ·4H 2 O, CAN(III))–formic acid.

Biodegradation of bisphenol A by cultured cells of Caragana chamlagu.

The biological degradation of 2,2-bis(4-hydroxyphenol)propane (1; bisphenol A, BPA), a representative endocrine disruptor, was studied with plant-cultured cells of Caragana chamlagu. An initial BPA concentration of 425 μM in an aqueous solution was degraded by C. chamlagu at 25°C for 2 days in the dark, and two intermediates were then completely dissipated after 10 days.

Biotransformation of (+)- and (-)-camphorquinones by plant cultured cells.

Biotransformation of (+)- and (-)-camphorquinones with suspension plant cultured cells of Nicotiana tabacum and Catharanthus roseus was investigated. It was found that the plant cultured cells of N. tabacum and C. roseus reduce stereoselectively the carbonyl group of (+)- and (-)-camphorquinones to the corresponding alpha-keto alcohols.

Synthesis of α,β-unsaturated ketone from α-iodo ketone using photoirradiation

Abstract Irradiation of α-iodo ketone in hexane under a nitrogen atmosphere with a high-pressure mercury lamp (λ>300nm) at room temperature afforded the corresponding α,β-unsaturated ketones in good yield. This reaction affords a new, clean and convenient synthetic method for the α,β-unsaturated ketone.

Oxidative cleavage of the C-C bond of 3,6-dialkylcyclohexane-1,2-diones by cell suspension cultures of Marchantia polymorpha

Biotransformation of 3,6-dialkylcyclohexane-1,2-diones by cell suspension cultures of Marchantia polymorpha involves regioselective oxidative cleavage of the C-C bond to give the corresponding oxocarboxylic acids shortened by one carbon unit. In the case of cyclohexane-1,2-dione, adipic acid was obtained.

Biotransformation of (±)-2-methylcyclohexanone by fungi

The biotransformation of 2-methylcyclohexanone (1) using 16 fungal strains and some mushroom cultures was investigated. Fusarium sp. was one of the effective biocatalysts for oxidoreduction of 2-methylcyclohexanone (1). cis-2-Methylcyclohexanol (2a) was isomerized to trans-2-methylcyclohexanol (2b) by Fusarium sp. In addition, the corresponding lactones 3 was obtained by Baeyer-Villiger oxidation using Fusarium sp. AP-2 (46%, 94% ee).

Preparative conversion of oximes to parent carbonyl compounds by cerium(IV) sulfate in acetonitrile and alcohol

A new method for the direct conversion of oximes into aldehydes and ketones by treatment with cerium(IV) salts is described. Cerium(IV) salts can be used as an effective and mild oxidizing agent for the regeneration of carbonyl compounds from oximes in good yield. The solvent effects are discussed.

Novel self-coupling reaction of cyclic ketones under a high-pressure mercury lamp

Abstract A novel self-coupling reaction in alcohol or hexane-water of cycloalkanone (cycloheptanone, cyclooctanone, and cyclododecanone) with irradiation under a high-pressure mercury lamp yielded the corresponding pinacol-type compound in good yields. In the case of cyclohexanone, 2-methyl-, 2-phenyl-, 4-methylcyclohexanone, 5α- and 5β-cholestan-3-one, the pinacol derivatives were not obtained and the dimethyl acetals were given.

Biotransformation of bromosesquiterpenes by marine fungi

Biotransformation of bromosesquiterpenes was investigated with two types of fungi, Rhinocladiella atrovirens NRBC 32362 and also Rhinocladiella sp. K-001, isolated from the Okinawan brown alga Stypopodium zonale. R. atrovirens NRBC 32362 converted aplysistatin 1 into three compounds 5alpha-hydroxyaplysistatin 4, 5alpha-hydroxyisoaplysistatin 5 and 9beta-hydroxyaplysistatin 6. Transformation of 1, palisadin A 2 and 12-hydroxypalisadin B 3 by Rhinocladiella sp. K-001 gave two compounds, 3,4-dihydroaplysistatin 7 and 9,10-dehydrobromopalisadin A 8.

Characterization of reaction products of several bis(β-diketonato)copper(II) compounds with 1H-pyrazoles. Adducts, DI- and tetranuclear complexes, and coordination polymers

Abstract When [Cu(L 1 ) 2 ] (HL 1 = aliphatic β-diketone with branched alkyl groups) and [Cu(L 2 ) 2 ] (HL 2 =aliphatic β-diketone with linear alkyl groups) were allowed to react with 1H-pyrazoles (Hpzl), tetranuclear complexes [Cu 4 (μ 4 -O)(L 1 ) 4 (μ-pzl) 2 ] and dinuclear complexes [Cu 2 (L 2 ) 2 (μ-pzl) 2 ] were produced respectively, but the reactions of [Cu(L 3 2 ] (HL 3 = aroyl- or heteroaroylacetone) with 1H-pyrazole (Hpz) gave coordination polymers [{Cu(L 3 )(μ-pz)} n ] and/or adducts [Cu(L 2 ) 2 (Hpz) n ] ( n = 1 and/or 2). The substituent effects of the β-diketonato ligands on the reaction products are discussed. The structure of one of the tetranuclear products Cu 4 (μ 4 -O)(dibm) 4 (μ-4-mpz) 2 ] (Hdibm = 2,6-dimethylheptane3,5-dione; 4-Hmpz = 4-methyl-1 H-pyrazole) has been determined by X-ray analysis. The structures of some of the other products are estimated on the basis of their IR and diffuse reflectance spectra.