Synthesis of fullerenyl-1,2,3-triazoles by reaction of fullerenyl azide with terminal acetylenes.

Fullerenyltriazoles were synthesized by the interaction of azidofullerene with terminal acetylenes, in which the heterocyclic fragment is directly attached to the fullerene core. The electrochemical studies of the synthesized triazole-containing fullerenes have proved that the potentials of the first reduction peaks are shifted to a less cathodic region compared to unmodified C. According to theoretical calculations, synthesized fullerene C derivatives can be considered as promising acceptor components of organic solar cells.

Cobalt(I)-Catalyzed [6π + 2π] Cycloaddition of 1,2-Dienes and 1,3-Diynes to -Carbocholesteroxyazepine in the Synthesis of Previously Undescribed Heterofunctional 9-Azabicyclo[4.2.1]nonadi(tri)enes.

Promising heterofunctional ()-9-azabicyclo[4.2.1]nona-2,4-dienes (79-92%) and 9-azabicyclo[4.

Synthesis and cytotoxic activity of unsaturated macrolides and their hybrid molecules with a C fullerene.

Previously unreported macrodiolides containing a 1Z,5Z-diene fragment in the structure have been synthesized with high yields and stereoselectivity by our research group, using the intermolecular esterification of malonic acid with α,ω-diols containing bis-methylene-separated Z-double bonds, catalyzed by Hf(OTf)4 hafnium triflate. Under Bingel-Hirsch conditions, the synthesized macrodiolides were chemically bonded with a C60 fullerene to produce the corresponding methanofullerenes. The cytotoxic activity of macrodiolides and methanofullerenes in relation to Jurkat, K562, U937, HL60 tumor cell lines and normal fibroblasts was studied.

Synthesis of Functionally Substituted Bicyclo[4.2.1]nona-2,4-dienes and Bicyclo[4.2.1]nona-2,4,7-trienes by Cobalt(I)-catalyzed [6π + 2π] Cycloaddition of 2-Tropylcyclohexanone.

The [6π + 2π] cycloaddition of 2-tropylcyclohexanone to allenes and alkynes was accomplished for the first time using the three-component catalytic system Co(acac)(dppe)/Zn/ZnI, thus giving previously unknown functionally substituted bicyclo[4.2.1]nona-2,4-dienes and bicyclo[4.

Total Synthesis of Natural Lembehyne C and Investigation of Its Cytotoxic Properties.

The first -stereoselective method for the synthesis of the natural marine alkynol lembehyne C, containing a 1,5,9-triene moiety, in 41% yield was developed using the new Ti-catalyzed cross-coupling of oxygenated and aliphatic 1,2-dienes as the key step. It was found for the first time that lembehyne C exhibits moderate cytotoxicity against Jurkat, K562, U937, and HL60 cancer cells and also efficiently induces apoptosis in Jurkat cells, with the cell death mechanism being activated by the mitochondrial pathway. The lembehyne C inhibition of the cell cycle follows the mitotic catastrophe mechanism.

New 1Z,5Z-diene macrodiolides: Catalytic synthesis, anticancer activity, induction of mitochondrial apoptosis, and effect on the cell cycle.

An original scheme was developed for the synthesis of previously undescribed unsaturated macrodiolides containing a 1Z,5Z-diene moiety in 44-80% yields and with high stereoselectivity (>95%) based on the intermolecular esterification of α,ω-diols with α,ω-alka-nZ,(n + 4)Z-dienedicarboxylic acids (1,12-dodeca-4Z,8Z-dienedicarboxylic acid, 1,14-tetradeca-5Z,9Z-dienedicarboxylic acid, 1,18-octadeca-7Z,11Z-dienedicarboxylic acid) catalyzed by hafnium triflate [Hf(OTf)]. The unsaturated dicarboxylic acids were prepared via homo-cyclomagnesiation of tetrahydropyran ethers of O-containing 1,2-dienes with EtMgBr in the presence of Mg metal and the CpTiCl catalyst (10 mol.%) and the subsequent Jones oxidation of pyran ethers formed after the acid hydrolysis of magnesacyclopentanes.

Comparative in vitro Studies of the Topoisomerase I Inhibition and Anticancer Activities of Metallated N-Confused Porphyrins and Metallated Porphyrins.

Using the original approach, a series of metallated N-confused porphyrins and metallated porphyrins have been synthesized and characterized. For all the synthesized porphyrins, in vitro studies of cytotoxic activity against K562, U937, HL-60, Jurkat, A549 and HeLa cancer cell lines, the ability to induce apoptosis and effects on the cell cycle as well as the kinetics of proliferative activity of porphyrins and their respective metallated complexes in real time have been developed. The inhibitory activity of metallated porphyrins against human topoisomerase I and the possible mechanism of inhibition have been carried out by modelling using molecular docking.

Synthesis and Electrochemical Properties of Fullerenylstyrenes.

An efficient preparative method was developed for the synthesis of previously unreported fullerenylstyrenes based on the reaction of C fullerene with terminal acetylenes and EtMgBr in the presence of Ti(O-Pr). The voltammetric curves of the prepared fullerenylstyrenes were studied, and good prospects for their application as acceptor materials for bulk heterojunction solar cell were demonstrated.

Synthesis of New Cu Complex Based on Natural 5,9-Eicosadienoic Acid: Effective Topoisomerase I Inhibitor and Cytotoxin against the Cisplatin-Resistant Cell Line.

The complex (bipy)Cu(5,9-eicd) was prepared by the reaction of Cu(OAc) with 5,9-eicosadienoic acid and 2,2'-bipyridine in methanol. The new copper complex showed high antitumor activity in vitro toward A2780cis, A2780, Hek293, K562, HL60, Jurkat, and U937 cell lines and efficiently inhibited human topoisomerase I. Using flow cytofluorometry, (bipy)Cu(5,9-eicd) was studied for the effect on the cell cycle and apoptosis-inducing activity in tumor cells.

Ti-Catalyzed Cross-Cyclomagnesiation of 1,2-Dienes in the Total ,,-Stereoselective Synthesis of Natural Acetogenin-Chatenaytrienin-1.

The first total synthesis of natural acetogenin, chatenaytrienin-1, was performed in 10 steps and in 41% overall yield using cross-cyclomagnesiation of (6)-heptadeca-1,2,6-triene and trideca-11,12-dien-1-ol tetrahydropyran acetal with EtMgBr in the presence of Mg metal and the CpTiCl catalyst (10 mol %) as the key step of the synthesis.

The Synthesis of Bicyclo[4.2.1]nona-2,4,7-trienes by [6π + 2π]-Cycloaddition of 1-Substituted 1,3,5-Cycloheptatrienes Catalyzed by Titanium and Cobalt Complexes.

The [6π + 2π]-cycloaddition of alkynes to 1-methyl-, propyl-, benzyl-, and hydroxymethyl-substituted 1,3,5-cycloheptatrienes in the presence of catalytic systems Ti(acac)Cl-EtAlCl and Co(acac)(dppe)/Zn/ZnI was performed for the first time to give practically valuable bicyclo[4.2.1]nona-2,4,7-trienes in high yields (72-88%).

Synthesis and Properties of Energy-Rich Methanofullerenes Containing Norbornadiene and Quadricyclane Moieties.

The energy-rich methanofullerenes were synthesized for the first time by the reaction of fullerene C with mono- and bisquadricyclane esters of malonic acid. The C-C bond cleavage in the quadricyclane moieties of new hybrid molecules takes place in the presence of catalytic amounts of Cu, Pd, and Pt salts or complexes or SiO and is accompanied by heat evolution.

Aminomethylation of Fullerene C with N,N',N″-Triaryl- or N,N',N″-Trihetaryl-1,3,5-perhydrotriazines in the Presence of EtMgBr and Ti(Oi-Pr).

A new method for the functionalization of fullerenes based on the reaction between in situ generated aryl- or hetaryl-containing 1,3,5-perhydrotriazines and EtMgBr in the presence of Ti(Oi-Pr) has been developed. The cleavage of the triazine ring under previously developed conditions1-6 results in the formation of aminomethylated derivatives of fullerene C with high yields (80-90%) and selectivity (∼90%).

Cobalt-Catalyzed [6 + 2] Cycloaddition of Alkynes with 1,3,5,7-Cyclooctatetraene as a Key Element in the Direct Construction of Substituted Bicyclo[4.3.1]decanes.

A new, effective catalytic system based on Co(acac) has been developed for [6 + 2] cycloaddition of terminal alkynes to 1,3,5,7-cyclooctatetraene to give substituted bicyclo[4.2.2]deca-2,4,7,9-tetraenes in high yields (68-85%).

Short Route to the Total Synthesis of Natural Muricadienin and Investigation of Its Cytotoxic Properties.

An original synthesis of the acetogenin muricadienin, the bioprecursor of solamin, has been developed. The key step in the five-step 41% overall yield synthesis is the catalytic cross-cyclomagnesiation reaction of functionally substituted 1,2-dienes with EtMgBr in the presence of Cp2TiCl2 and magnesium metal. It has been demonstrated for the first time that muricadienin exhibits a moderate in vitro inhibitory activity against topoisomerases I and IIα, key cell cycle enzymes.