Syntheses and antitumor activities of N6,N6-dimethyladenosine carboxylate analogues

Several analogues substituted with fatty acid at the 2'-, 3'-, or 5'-position of the ribose moiety of N6,N6-dimethyladenosine were synthesized and tested for antitumor activity against cultured cells of L1210 leukemia and/or Ehrlich ascites. The cytotoxicity and increase of life span obtained with congeners in the N6,N6-dimethyladenosine 3'- or 5'-substituted series were comparable to in vitro or several times better in vivo than those of the mother compound.     

Enantioselective Strecker-type reaction to sulfonylimines having a 2-pyridylsulfonyl group as a novel stereocontroller

A catalytic enantioselective Strecker-type reaction to N-(2-pyridylsulfonyl)imines in the presence of chiral bis(oxazoline)s afforded the products with a high enantioselectivity. A dynamically induced new chiral center on the sulfur by discriminative coordination of a chiral Lewis acid to one of the sulfonyl oxygens efficiently controlled the enantioselectivity.     

Asymmetric 1,4-addition of alkenylzirconium reagents to α,β-unsaturated ketones catalyzed by chiral rhodium complexes

Highly enantioselective 1,4-addition of alkenylzirconocene chlorides to α,β-enones was found to be catalyzed by a chiral rhodium complex generated from [Rh(cod)(MeCN)₂]BF₄ and (S)-BINAP. The reaction can be applied to either cyclic or acyclic enones and the optical yield was up to 99% ee. The reaction mechanism would involve the transmetalation between the alkenylzirconocene chloride and the rhodium complex to give the alkenylrhodium species as a key intermediate.     

Dipole moments of (styrene-p-chlorostyrene) triblock copolymers in solutions

(Styrene-p-chlorostyrene) triblock copolymers of the ABA and BAB types (A—polystyrene; B—poly-p-chlorostyrene) were prepared by anionic polymerization and their conformational behaviours in solutions were studied from measurements of the dipole moments. Two solvents, toluene and cumene, were used for the study; toluene is a good solvent for both polystyrene and poly-p-chlorostyrene whereas cumene is a selective solvent, good for polystyrene but poor for poly-p-chlorostyrene. It was found that the dipole moments of the block copolymers measured in toluene are the same for the ABA and BAB copolymers; in cumene however the dipole moment of the BAB copolymer is smaller than that of the ABA copolymer. The results give an additional support to our previous conclusion that the conformation of the block copolymers in a good solvent such as toluene could be approximated with a pseudo-random coil form; in a selective solvent, however, some anomalies take place in the conformation of the block copolymers, as deduced from intrinsic viscosity, osmotic pressure and light scattering measurements.     

Determination of molecular weight distribution of nylon 12 by gel permeation chromatography

Molecular weight distribution of Nylon 12 was determined with hexafluoroisopropanol/toluene mixture as eluent by gel permeation chromatography. Calibration curve for Nylon 12 was easily obtained from that of polystyrene because the method of universal calibration was applicable among these polymers. The molecular weight distributions of Nylon 12 were always broader than expected by the theory of polymerization, i.e., most probable distribution. This result was not caused by broadening effect in gel permeation chromatography, but by polymerization itself.     

Synthesis and antifungal activities of a series of (1,2-disubstituted vinyl)imidazoles.

A series of vinylimidazoles containing a hetero atom such as sulfur or oxygen at a beta-position of the vinyl group was prepared and the antifungal activities were tested. It was found that sulfur-substituted derivatives such as (E)-1-[2-(methylthio)-1-[2-(pentyloxy)phenyl]ethenyl]-1H-imidazole (5a-5) and (E)-1-[1-[2-(hexyloxy)phenyl]-2-(methylthio)ethenyl]-1H-imidazole (5a-6) showed excellent antifungal activities against dermatophytes and yeast cells. The stereochemistry of the hydrochloride salt of 5a-5 was determined by X-ray crystallography. The structure-activity relationships were discussed.