Total syntheses of (-)- and (+)-goniomitine

The Stille coupling reaction of 3-(benzyloxymethyl)-1-(tert-butyldiphenylsiloxy)ethyl-1-(tributylstannyl)allene with N-(tert-butoxycarbonyl)-2-iodoaniline directly produced the corresponding 2-vinylindole derivative, which was independently transformed into natural (-)-goniomitine and unnatural (+)-goniomitine via the cross-metathesis with chiral oxazolopiperidone lactams. The antiproliferative activity of the synthesized natural (-)-goniomitine in Mock and MDCK/MDR1 cells showed them to be more potent to retard cell growth than unnatural (+)-goniomitine.     

Ring-opening polymerization of six- and seven-membered cyclic pseudoureas

The cationic ring-opening polymerization of six-membered cyclic pseudoureas, 2-(1-pyrrolidinyl)- ( 2a ) and 2-morpholino-5,6-dihydro-4H-1,3-oxazine ( 2b ), was examined, which proceeded in two different ways, depending on the nature of initiator. The polymerization of 2 with methyl p-toluenesulfonate or trifluoromethanesulfonate (MeOTf) produced poly[(N-carbamoylimino)trimethylene], while that with benzyl chloride or bromide or methyl iodide gave a polymer consisting of 1,3-diazin-2-one-1,3-diylalkylene unit (the main component) and (N-carbamoylimino)trimethylene unit. The cationic ring-opening polymerization of seven-membered cyclic pseudourea, 2-(1-pyrrolidinyl)-4,5,6,7-tetrahydro-4H-1,3-oxazepine ( 3 ) was also examined. The polymerization of 3 with MeOTf as initiator gave poly{[N-(1-pyrrolidinycarbonyl)imino]tetra-methylene}. With benzyl chloride, on the other hand, no polymerization of 3 proceeded but, instead, the quantitative isomerization of 3 to 1,1′-carbonyldipyrrolidine took place. The polymerization mechanism of 2 and 3 as well as the isomerization mechanism of 3 were discussed with comparing them to the polymerization mechanism of five-membered pseudoureas. © 1977 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 933–945, 1997     

Investigations on poly(vinyl chloride). IV. Effects of metal chlorides on the thermal decomposition of poly(vinyl chloride)

The effects of various metal oxides upon the thermal decomposition of poly(vinyl chloride) (PVC) were previously reported. In this work, 23 metal chlorides were investigated to determine their effects on the thermal decomposition of PVC by pyrolysis–gas chromatography at 500°C. Each metal chloride exhibits influences on the course of thermal decomposition of PVC almost similar to the corresponding metal oxide except for a few elements; the metal chlorides from acidic metal oxides accelerate the thermal decomposition of PVC, but the metal chlorides from basic metal oxides do not. On comparing the effects of metal oxides and metal chlorides on the thermal decomposition of PVC, most metal chlorides were found to accelerate the thermal decomposition of PVC more than the corresponding metal oxides, owing to ease of addition of the chlorine atoms released from metal chloride to the dehydrochlorinated chains. It is concluded from these results that the thermal decomposition of PVC containing metal salts is markedly influenced by the ease with which chlorine atoms are released from the corresponding metal chloride.     

Structure and chemical behavior of an organoaluminum compound [Rb2AlOCR′NPh]2, a stereospecific catalyst for polymerization of acetaldehyde

A series of organoaluminum compounds [R₂AlOCR′NPh]₂, which are the reaction products between trialkylaluminum compounds and secondary acid amides and are excellent catalysts for stereospecific polymerizations of aldehydes, were isolated in the crystalline state. Chemical behavior of such compounds toward Lewis acids and bases were interpreted in terms of the structures of [Me₂AlOCPhNPh]₂ and its trimethylamine oxide complex Me₃NO·AlMe₂OCPhNPh which were determined by X-ray structure analyses. Reaction products of primary and tertiary acid amides with trialkylaluminum compounds were also studied.     

Conjugated‐Protein Mimics with Molecularly Imprinted Reconstructible and Transformable Regions that are Assembled Using Space‐Filling Prosthetic Groups

Conjugated‐protein mimics were obtained using a new molecular imprinting strategy combined with post‐imprinting modifications. An antibiotic was employed as a model template molecule, and a polymerizable template molecule was designed, which was composed of the antibiotic and two different prosthetic groups attached through a disulfide bond and Schiff base formation. After co‐polymerization with a cross‐linker, the template molecule was removed together with the prosthetic groups, yielding the apo‐type scaffold. Through conjugation of the two different prosthetic groups at pre‐determined positions within the apo‐type scaffold, the apo cavity was transformed into a functionalized holo cavity, which enables the on/off switching of the molecular recognition ability, signal transduction activity for binding events, and photoresponsive activity.     

UNIQUE DNA REPAIR PROPERTY OF AN ULTRAVIOLET-SENSITIVE (radC MUTANT OF Dictyostelium discoideum

Abstract— Dictyostelium discoideum is an organism that shows higher UV resistance than other organisms, such as Escherichia coli and human cultured cells. We examined the removal of cyclobutane pyrimidine dimers (CPD) and 6–4 photoproducts from DNA in the radC mutant and the wild-type strain using an enzyme-linked immunosorbent assay with monoclonal antibodies. Wild-type cells excised more than 90% of both CPD and 6–4 photoproducts within 4 h. Dictyostelium discoideum appeared to have a special repair system, because 6–4 photoproducts were repaired faster than CPD in E. coli and human cultured cells. In radC mutant cells, although only 50% of CPD were excised from DNA within 8 h, effective removal of 6–4 photoproducts (80% in 8 h) was observed. Excision repair-deficient mutants generally cannot remove both CPD and 6–4 photoproducts. Though the radC mutant shows deficient excision repair, it can remove 6–4 photoproducts to a moderate degree. These results suggest that D. discoideum has two kinds of repair systems, one mainly for CPD and the other for 6–4 photoproducts, and that the radC mutant has a defect mainly in the repair enzyme for CPD.     

Chirality transfer during alkylation of chiral amides

Chiral amides derived from O-methyl mandelic acid and achiral amines underwent enantioselective alpha-methylation on treatment with LTMP followed by addition of methyl iodide; chirality transfer from an undeprotonated chiral amide into an achiral enolate in a mixed aggregate is supposed to be responsible for the asymmetric induction.     

Ferroelectric properties of vinylidene fluoride copolymers

Ferroelectric properties of copolymers of vinylidene fluoride with trifluoroethylene and tetrafluoroethylene are described with special interest in their polarization reversal and phase transition behavior. The ferroelectric phase consists of all-trans molecules packed in a parallel fashion while molecules adopt irregular TT, TG, T[Gbar] conformations in the paraelectric phase. In the ferroelectric phase, polarization reversal occurs at very high fields (> 100 MV/m) as a result of eventual 180° rotations of individual chain molecules around their axes. The switching time ranges from sec to nsec depending upon the strength of the applied field according to an exponential law with a particularly large activation field (～ 1 GV/m). The value of the observed remnant polarization is consistent with prediction from a simple dipole sum implying a minor contribution from the Coulomb interaction. The ferroelectric-to-paraelectric transition appears most clearly for copolymers containing 50-80 mol% vinylidene fluoride at temperatures from 70 to 140°C. The transition accompanies cooperative dipole motions associated with elementary trans-gauche transformations. Changes in various properties as well as in structures in the vicinity of the Curie point are consistent with an order-disorder transition of first order. Detailed characteristics specifying their ferroelectricity are summarized and discussed in relation to the molecular, crystalline, and higher-order structures inherent to ferroelectric polymers.