Fumio Hino

Palladium-catalyzed meso-amination and amidation of porphyrins: marked acceleration with the Ni(II) central metal ion

The preparation of meso-amino and meso-amido substituted porphyrins was easily accomplished by palladium-mediated cross-coupling reactions of meso-brominated porphyrins with amines and amides. Ni(II) introduced as a central metal ion into the substrate porphyrin markedly accelerated the cross-coupling.

Palladium-catalyzed Kumada coupling reaction of bromoporphyrins with silylmethyl Grignard reagents: preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems.

We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH(2)OH, CH(2)OMe, and CH(2)F functionalities and the fluoride ion-mediated desilylative introduction of carbon-carbon single and double bonds.

A Simplified Method for Detecting Isoniazid Compliance in Patients Receiving Antituberculosis Chemotherapy

The objective of this study was to develop a new simplified method using thin‐layer chromatography (TLC) for determining isoniazid (INH) compliance in patients receiving antituberculosis chemotherapy. TLC was performed on silica gel plates using a standard solution of INH and acetylisoniazid (AcINH) and ethyl acetate‐methanol (70:30 v/v) as the developing solvent. The spots of compound were detected by iodine. In the human study, fractional urine samples were collected over 24 hours from 4 healthy human subjects genotyped for NAT2 and to whom 400 mg of INH were administered orally. These samples were used for TLC analysis. The results of TLC were compared with those of high‐performance liquid chromatography (HPLC). This method indicated good separation between INH and AcINH in standard solutions. The detection limits for INH and AcINH (applied volume; 20 μl of standard solution) were 2.2 nmole and 5 nmole, respectively, as detected by iodine. In the human study, the INH spot in urine was not detected on the TLC plate, except in one sample over the 0‐ to 4‐hour period from 1 volunteer. However, the AcINH spot was detected in all urine samples from all volunteers. The total experimental time from application of the urine sample to analysis on TLC was 30 minutes. The results suggest that this method for detecting AcINH on TLC is an excellent, convenient, and simple method for determining INH compliance in patients receiving standard antituberculosis chemotherapy regimen or INH preventative therapy, regardless of the patients NAT2 genotype.

Base promoted oxidative decarboxylation of ethyl phenylglycinate via oxaziridine

Abstract Base catalyzed decompositions of 2-(α-ethoxycarbonyl-benzyl)-3-phenyl-oxaziridines carried out in benzene in an atmosphere of oxygen yielded N-benzoyl benzamides along with ethyl phenylglyoxylate imine and benzaldehydes.

Metalloporphyrin-catalysed rearrangement of oxaziridines: an efficient and regioselective synthesis of lactams using ring-enlargement of N-phenyl-spirooxaziridines

Manganese(III) tetraphenylporphyrin, Mn(tpp)Cl, is a new and specific catalyst for stereo- and regio-selective rearrangement of N-phenyl-spirooxaziridines into lactams.