DNA-bleomycin interaction: Nucleotide sequence-specific binding and cleavage of DNA by bleomycin

Biosynthetic intermediates and synthetic analogues of bleomycin (BLM) have been investigated for their metal binding, dioxygen activation, and DNA cleavage. Molecular O₂ was activated by the Fe(II) complex of a synthetic model ligand. Nucleotide sequence specificities in DNA cleavage by the BLM-Fe(II) and deglyco-BLM-Fe(II) complexes were almost identical. It has been shown that (1) the β-aminoalanine-pyrimidine-β-hydroxyhistidine portion of BLM is essential for the metal binding and dioxygen activation and (2) the bithiazole moiety contributes to the specific binding to guanine base of DNA.     

Formation of cyclic organosilicon compounds via organopolysilyl anions starting from methoxymethyldisilanes. A mechanistic study

In the presence of a catalytic amount of sodium methoxide, sym-dimethoxytetramethyldisilane was converted into α,ω-dimethoxypermethylpolysilanes, MeO(SiMe₂)_nOMe where n ? 3, at room temperature. On the other hand, similar treatment of the disilane in THF solution gave cyclic polysilanes, (Me₂Si)_n where n = 5–7. Decomposition of the disilane in the presence of diphenylacetylene afforded a trisilacyclopentene derivative under similar conditions. This compound was obtained also by the reaction between α,ω-dimethoxypermethylpolysilanes and diphenylacetylene in the presence of sodium methoxide. These cyclic products most likely were formed via permethyl polysilyl anion intermediates derived from α,ω-dimethoxypermethylpolysilanes. Also, the formation of α,ω-dimethoxypermethylpolysilanes could be elucidated in terms of the mechanism involving the base-assisted, concerted nucleophilic substitution or stepwise substitution by silyl anions, rather than the successive dimethylsilylene (Me₂Si:) insertion reaction.     

Reactions of 1,2-dimethoxytetramethyldisilane with styrenes: Formation of a new type of silacyclopentanes having phenyl substituents on ring carbons

The reaction of 1,2-dimethoxytetramethyldisilane with styrene and α-methylstyrene in the presence of NaOMe catalyst in tetrahydrofuran (THF) gave the new silacyclopentanes 1,1-dimethyl-2,4-diphenyl-1-silacyclopentane (IIIa) and 1,1,2,4-tetramethyl-2,4-diphenyl-1-silacyclopentane (IIIb), respectively. These silacyclopentanes were found to exist as cis-trans mixtures. The use of sodium metal in place of NaOMe afforded similar results. Reactions of a polysilane mixture, MeO-(SiMe₂)_nOMe (n ≧ 3), with the styrenes also gave similar results. In some cases, polysilacycloalkanes such as 1,2,3-trisilacyclopentanes (IV) and 1,2,3,4-tetrasilacyclohexanes (V) were obtained as by-products. A mechanism for the formation of the silacyclopentanes and polysilacycloalkanes is presented. It was found that electron impact decomposition of silacyclopentanes IIIa and IIIb, trisilacycloalkane IV and tetrasilacycloalkane V gave molecular ions corresponding to the silacyclopropane, cyclotrisilane and cyclotetrasilane systems.     

Regio-specific total synthesis of (±)-2-hydroxyaklavinone

The tricyclic quinone 8 was successfully synthesized from naphthazalin, and the total synthesis of (±)-2-hydroxyaklavinone via 8 was accomplished in an overall yield of about 18% through the regio-controlled route.     

Reactions of hydropolysilanes with alcohols catalysed by tris(triphenylphosphine)chlororhodium

[RhCl(PPh₃)₃] is a very effective catalyst for the cleavage of Si-Si bonds by alcohols.     

Addition of chlorodisilanes to 1,3-butadienes in the presence of tetrakis(triphenylphosphine)palladium(0). A facile route to (Z)-1,4-bis(chlorosilyl)but-2-enes

In the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0), chlorodisilanes of type Me_nSi₂Cl_6-n (n  0, 2, 3 and 4) add to 1,3-butadienes to give (Z)-1,4-bis(chlorosilyl)but-2-enes.     

Thermal hysteresis and thickness dependence of the molecular orientation of poly(di-n-hexylsilane) in the film state

Molecular orientation of poly(di-n-hexylsilane) adsorbed on poly(vinyl alcohol) film has been studied by making use of the stretching technique. Dichroic ratio, Rd, strongly depended on the thickness of poly(di-n-hexylsilane) thin film and the highest value ca. 19 was observed at the film thickness of 110 +/- 30 nm. The thermal hysteresis of the molecular orientation was observed in the heating-cooling cycles. By studying the fluorescence spectrum it was confirmed that a portion of the poly(di-n-hexylsilane) molecules were in transoid conformation even at 320 K, although most of poly(di-n-hexylsilane) molecules were in disordered conformation (conformation D). This poly(di-n-hexylsilane) in transoid conformation is formed in the stretching process and may play a role of crystallization nucleus to induce the whole orientation of the poly(di-n-hexylsilane) in the film state.     

The structure of a novel inhibitor of dextransucrase

The structure of ribocitrin ($\text{I}$), a novel dextransucrase inhibitor produced by a $\text{Streptomyces}$ was elucidated to be 2-(S)-[O-α(-D-ribofuranosyl-(l→2)- O-α-D-ribofuranosyl- (1→3)-α-D-ribofuranosyloxyl -1,2,4-butanetricarboxylic acid.     

Stekeospecific transformation of D-sugar to L-sugar in complex aminoglycoside. Synthesis of a kanamycin B analog having 2,6-diamino-2,4,6-trideoxy-L-arabino-hexopyranose

A 4′-ene derivative of kanamycin B ($\text{4}$) was derived from the epoxide ($\text{1}$) by oxidative elimination of the 4′-phenylseleno group into the allylic alcohol ($\text{3}$). The title compound, 0-(2,6-diamino-2,4,6-trideoxy-β-L-arabino-hexopyranosyl)-(1→4)-0-[3-amino-3-deoxy-α-D-glucopyranosyl-(1→6)]-2-deoxystreptamine ($\text{6}$) was obtained from $\text{4}$ by stereospecific hydrogenation followed by removal of the masking groups, changing the D-sugar moiety of the 4-0-glycoside portion into an L-sugar.     

Total synthesis of the disaccharide of bleomycin, 2-0-(α-D-mannopyranosyl)-L-gulopyranose

2-0-(α-$\text{D}$-Mannopyranosyl)-$\text{L}$-gulopyranose, the sugar portion of bleomycin has been synthesized.