Home – Home – Jornals – Chemistry for Sustainable Development 2008 number 6

Application of methylpheophorbyde а as an initial compound for the synthesis of potential anticancer agents is considered. The possibility to carry out a number of reactions participated by the main reaction centres of methylpheophorbyde а (exocycle, vinyl group, propionate substituent) for preparative purposes is shown. The use of the reactions of the main centres provides the possibility to obtain porphyrin compounds of diverse structures. All the synthesized compounds have a chlorine pharmacophore in the molecule, which ensures their activity as photosensitising agents for photodynamic therapy of oncological and other diseases.

Some directions and results of investigations in the area of metal complex catalysis initiated by Academician G. A. Tolstikov are considered, along with the new directions being successfully developed at present by his followers. The main attention is paid to reactions, efficient reagents and promising preparative methods of metal complex catalysis in organic and organometallic synthesis.

Chemical aspects of epoxidation, ecological safety of the promising methods of processing renewable raw material - terpenes - are the main focuses of the present review. Various epoxidation systems are considered, first of all those allowing one to perform the catalytic epoxidation of terpenes; their promising character with respect to the introduction into industry is evaluated. The data published during the years 1988 to 2008 are included in the review. All the data are arranged in common tables for convenience of comparing different epoxidation systems and choosing optimal process conditions.

Selective transformations of triterpene glycoside (glycyrrhizic acid), which is the main biologically active component of the roots of (Glycyrrhiza glabra L.) and (Gl. uralensis Fisher) at the carbohydrate chain and/or aglycon were carried out. New groups of biologically active compounds valuable for medicine were obtained (amides, glycopeptides, pyrazoles, conjugates with aminosaccharides, triterpene glycosides), possessing high anti-inflammatory, antiulcerogenic, immunopotentiating and antiviral activity. It was established that chemical modification of glycyrrhizic acid by adding amino acids, dipeptides and amino saccharides into the carbohydrate part of its molecule opens the outlooks for the synthesis of new stimulants of the humoral immune response, antiHIV-1-, antoSARS CoV- and antiEBV-agents.

Results of investigations into the synthesis of prostanoids and eleuthesides based on saccharides of levoglucosan and levoglucosenone, sesquiterpenoid (+)-δ-cadinol and diterpenoid isocembrol are generalized.

History of discovery and application of Dzhemilev reaction is discussed. This reaction is a catalytic cycloalumination, cyclo- and ethylmagnesiation of olefins, allenes, acetylenes with the help of alkyl and halogenoalkyl derivatives of Al and Mg with the participation of Ti-, Zr- and Co-containing catalysts. As a result of this reaction, new classes of cyclic organometallic compounds of non-transition metals (metametals) were obtained: aluminacyclopropanes, aluminacyclopropenes, aluminacyclopentanes, aluminacyclopentenes, aluminacyclopenta-2,4-dienes, magnesacyclopentanes, magnesacyclopentenes, magnesacyclopenta-2,4-dienes.

Possibility to use 4-methyltetrahydropyrane, mint and castor oil for the synthesis of low-molecular bioregulators of insects and for the development of biologically active preparations for beekeeping on the basis of synthetic metabolites of honey bees (Apis mellifera L.) is investigated.

Outlooks for the use of triterpenoids of lupane series in medical practice are discussed. Among native compounds, especially important one is betulic acid, a highly efficient anti-cancer agent and inhibitor of ЕСНО6 enterovirus. The most promising semi-synthetic derivatives of lupane series are amides, ureides, dipeptides and acylates of betulic, betulonic and 3-oximinonetulonic acids possessing high anti-HIV activity, pronounced anti-tumour and organ-protecting action. It is shown that the production of biologically active additives with betuline extract is actively developing.

Natural terpenes (+)-3-carene and α-pinene are widely used in the synthesis of biologically active substances. On the basis of the products of their ozonolytic splitting, synthesis schemes were developed for juvenoids, pheromones, pyrethroids. In the present work we propose a new efficient approach to the synthesis of pheromones and juvenoids with cyclopropane and cyclobutane rings in the molecule by means of ozonation of α,β-unsaturated ketones carenone and verbenone, which are easily obtained from (+)-3-carene and α-pinene. The mechanism of formation of 2,2-dimethyl-3-acetylcyclobutanecarboxylic acid - synton is the synthesis of the pheromone of grape mealybugs - is proposed.

Original schemes of the synthesis of known anti-HIV preparations azidothymidine and
2',3'-didesoxy-2',3'-didehydrothymidine (D₄T) are reported. The possibility to use the silyl method in the synthesis of glycosides of biologically active nitrogen-containing heterocycles is demonstrated.

By means of controllable ozonolysis of acyclic, cyclic and bicyclic alkenes and polyenes of regular structure and given configuration through dosing the calculated amount of ozone, followed by controllable decomposition of the peroxide products of ozonolysis, polyfunctional aliphatic and heterocyclic compounds, α,ω-bifunctional unsaturated compounds of the required (Z)- or (E)-configuration were synthesized. The routes of transformations of ozonolysis products were proposed for the synthesis of insect pheromones, juvenoids, acyclic terpenoids, tocopherols, ecdysteroids and their analogs.

Results of the joint investigations carried out at N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry and at the St. Petersburg branch of the Institute of Catalysis of the Siberian Branch of RAS on the development of scientific foundations of the design of postmetallocene catalytic systems of aryl imine type during the recent decade are generalized. Postmetallocene complexes with the structures providing high activity at a temperature within 70-90 °C and the possibility of their use for the synthesis of high-molecular polyethylene in gas-phase polymerisation were obtained for the first time.

Literature data describing the development of one-stage methods to synthesize strained polycyclic hydrocarbons involving metal complex catalysts are generalized. These methods are based on the reactions of homo- and cross-cyclization of norbornadiene and its derivatives with olefins, 1,2-dienes, 1,3-dienes and acetylenes. The synthesis of tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca- and dodecacyclic strained hydrocarbons, difficult to be synthesized with the help of other methods, was carried out using these reactions.

Modern methods of chemical transformations of available plant alkaloids aimed at obtaining pharmaceutically valuable agents are considered.