Synthetic approaches to N(delta)-methylated L-arginine, N(omega)-hydroxy-L-arginine, L-citrulline, and N(delta)-cyano-L-ornithine

Nomega-Methylated arginines such as asymmetric dimethyl-L-arginine (ADMA) and monomethyl-l-arginine (NMMA) are known as potent physiological inhibitors of nitric oxide synthases (NOSs). To explore a possible physiological and pharmaceutical relevance of N(delta)-methylated analogues, a synthetic scheme had to be developed that would not lead to N(delta)-methyl-L-arginine only but also to its presumed metabolites of NOS catalysis. Two basic synthetic approaches have been pursued to obtain N(delta)-methylated derivatives of L-ornithine, L-citrulline, L-arginine, and N(omega)-hydroxy-L-arginine. A first attempt utilized conventionally protected L-ornithine, i.e., the tert-butyl ester and Boc-amine, and led to three end compounds in excellent yields. Simultaneous protection of the alpha-amino acid moiety by formation of boroxazolidinones, particularly by employing 9-borabicyclo[3.3.1]nonane (9-BBN-H), proved to be a convenient option to perform side chain modifications and led to all of the desired end compounds. Additionally, enantiomeric excess (ee, %) of crucial synthetic intermediates and end compounds was determined by chiral HPLC.     

Copper(II) complexes of 2-formyl-, 2-acetyl- and 2-benzoyl-pyridine N(4)-phenyl-, N(4)-o-methoxyphenyl-, N(4)-p-methoxy-phenyl- and N(4)-p-nitrophenylthiosemicarbazones

Summary Cu^II complexes of 2-formyl-, 2-acetyl- and 2-benzoylpyridine N(4)-phenyl-, N(4)-o-methoxyphenyl-, N(4)-p-methoxyphenyl- and N(4)-p-nitrophenyltniosemicarbazones, coordinated either as neutral or monoanionic ligands, have been prepared and characterized. I.r., electronic and e.p.r. spectra of the complexes, as well as ¹H-and ¹³C-n.m.r. spectra of the thiosemicarbazones, have been obtained. Both the thiosemicarbazones and their complexes show either modest or no growth inhibitory activity against Paecilomyces variotii. However, some of these thiosemicarbazones possess significant activity against a number of tumour cell strains.     

N,N′-Bis(trimethylsilylmethyl)thiocarbamide and N,N′-Bis(trimethylsilylmethyl)-λ6-thiocarbamide S,S-Dioxide

N,N′-Bis(trimethylsilylmethyl)-λ⁶-thiocarbamide S,S-dioxide was synthesized by oxidation of N,N′-bis(trimethylsilylmethyl)thiocarbamide with hydrogen peroxide. The synthesized dioxide is a less active reducing agent than previously studied S,S-dioxides of organosilicon thiocarbamides in which the silicon atom is separated from the thiocarbamide fragment by a -CH₂CH₂CH₂- bridge.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 912–914.Original Russian Text Copyright © 2005 by Vlasova, Grigor’eva, Voronkov.     

二硝酸(N,N,N',N'-四正丁基丁二酰胺)合铀(Ⅱ)酰配合物的合成和结构

合成的配合UO~2[Bu~2NCO(CH~2)~2CONBu~2](NO~3)~2的晶体属四方晶系,a=b=3.3207(8),c=1.0711(4)nm,α=β=γ=90.00(0)°,V=11.811(7)nm^3,D~c=1.65g.cm^-3,Z=16,空间群为14~1/\α.配合物分子中铀酰离子由六个氧原子配位,其中四个来自两个硝酸根,另外两个来自有机配体的两个羰基,两个硝酸根被七原子环排斥而挤在一边,以铀原子为中心的六方双锥结构受到扭曲.     

Copper(II) complexes of 2-formyl-,2-acetyl- and 2-benzoylpyridine N(4)-o-, N(4)-m-, N(4)-p-chlorophenylthiosemicarbazones

Summary Cu^II complexes of 2-formyl, 2-acetyl- and 2-benzoylpyridine N(4)-o-, N(4)-m- and N(4)-p-chlorophenylthiosemicarbazones, coordinated either as a neutral or monoanionic ligand, have been prepared and characterized. I.r., electronic and e.s.r. spectra of the complexes, as well as ¹H- and ¹³C-n.m.r. spectra of the thiosemicarbazones, have been obtained. Both the thiosemicarbazones and their Cu^II complexes show either modest or no growth inhibitory activity against Paecilomyces variotii. Some of the thiosemicarbazones demonstrated significant activity against tumour cell strains.