U. M. Dzhemilev

Hydroamination of conjugated dienes catalyzed by transition metal complexes

The review summarizes published data on the hydroamination of 1,3-dienes with various primary and secondary amines, ammonia, and ammonium salts of mineral acids in the presence of transition metal complexes under homogeneous conditions. The effects of the nature of metal, ligand, initial diene, and amine and reaction conditions on the selectivity of hydroamination are considered, and possible reaction mechanisms are discussed.

Furfuryl Alcohol in Synthesis of Levulinic Acid Esters and Difurylmethane with Fe and Rh Complexes

The possibility of synthesis of levulinic acid esters by the reaction of furfuryl alcohol with aliphatic alcohols in the system CCl4-Fe(acac)3 was studied.

Manganese compounds in the catalysis of organic reactions

The review summarizes published data on the use of manganese compounds as catalysts in oxidation of alkanes, alcohols, aldehydes, sulfides, and amines and carbometalation, cross coupling, telomerization, chlorination, hydrosilylation, hydrohydrazination, and other reactions.

The facile synthesis of the 5Z,9Z-dienoic acids and their topoisomerase I inhibitory activity

An original, effective approach to the synthesis of natural and synthetic 5Z,9Z-dienoic acids in high yields (61-67%) and with high selectivity (>98%) was developed. The approach is based on the use of the new intermolecular catalytic cross cyclomagnesiation of terminal aliphatic and oxygenated 1,2-dienes upon treatment with Grignard reagents in the presence of the Cp2TiCl2 catalyst. High activity of (5Z,9Z)-5,9-eicosadienoic acid as a human topoisomerase I inhibitor at concentrations above 0.1 μM was elucidated.

Stereoselective synthesis of 11-phenylundeca-5Z,9Z-dienoic acid and investigation of its human topoisomerase I and IIα inhibitory activity.

(5Z,9Z)-11-Phenylundeca-5,9-dienoic acid was stereoselectively synthesized, based on original cross-cyclomagnesiation of 2-(hepta-5,6-dien-1-yloxy)tetrahydro-2H-pyran and buta-2,3-dien-1-ylbenzene with EtMgBr in the presence of Cp2TiCl2 catalyst giving 2,5-dialkylidenemagnesacyclopentane in 86% yield. The acid hydrolysis of the product and the Jones oxidation of the resulting 2-{[(5Z,9Z)-11-phenylundeca-5,9-dien-1-yl]oxy}tetrahydro-2Н-pyran afforded (5Z,9Z)-11-phenylundeca-5,9-dienoic acid in an overall yield of 75%. A high inhibitory activity of the synthesized acid with respect to human topoisomerase I (hTop1) and II (hTop2α) was determined.

First preparative synthesis of alumocyclopentanes involving zirconium complexes

M. Dzhemilev, A. G. Ibragimov, A. P. Zolotarev, R. R. Muslukhov, and G. A. Tolstikov UDC 542.97:547.514+547.256.2 We have recently published several communications on the carbometallation of ~-olefins using diethylmagnesium in the presence of catalytic amounts of Cp2SrCI 2 [i, 2]. Diethylalu ~ minum chloride by the action of TiCI~ or Ti(OBu) 4 [3], and triethylaluminum with two-compon- ent catalysts consisting of Cp2ZrCI 2 + 6Et2Mg or Cp2ZrCI 2 + 6(i-Bu)3Al [3]. In a continuation of a study of these reactions, we have established that, in contrast to the Cp2ZrCI 2 + 6Et=Mg catalyst, the reaction of Et3AI with ~-olefins, such as l-hexene, l-octene, and l-undecene, in the presence of Cp2ZrCl 2 taken in Et3Al:e-olefin:Cp2ZrCl 2 mole ratio equal to (100-120):100:2 at about 20~ over 6-8 h gives the corresponding alumocyclo- pentanes (Ia)-(!c) in 80-95% yields with high selectivity. Datta et al. [4] have proposed that the formation of alumocyclopentanes under the reac- tion conditions proceeds through the formation of zirconocyclopentanes according to scheme: EhAI q- Cp2ZrCl2 /- /\/\/--R -. C~Zr

Synthesis of lupane triterpenoids with triphenylphosphonium substituents and studies of their antitumor activity

New derivatives of lupane triterpenoids, viz., 20,29-dihydrobetulinic and 3-epi-20,29-dihydrobetulinic acid derivatives containing triphenylphosphonium fragments as substituents were synthesized. These compound considerably exceed betulinic acid in antitumor activity.

Oxidation of fullerenes with ozone

Heterophase and liquid-phase oxidation reactions of fullerene with ozone and the data on chemiluminescence generated in these reactions were considered and classified for the first time.

Effective synthesis of N-aryl-substituted 1,5,3-dithiazepinanes and 1,5,3-dithiazocinanes

Selective methods were developed for the synthesis of N-aryl-1,5,3-dithiazepinanes and N-aryl-1,5,3-dithiazocinanes by transamination of N-tert-butyl-1,5,3-dithiazepinane or recyclization of 1-oxa-3,6-dithiacycloheptane and 1-oxa-3,7-dithiacyclooctane by the action of aniline derivatives in the presence of Sm(NO3)3·6H2O catalyst.

Multicomponent condensation of aliphatic amines with formaldehyde and hydrogen sulfide

Cyclothiomethylation of primary aliphatic amines with the reagent H2S-CH2O (2:3) in aqueous medium mainly gave substituted dithiazines; oxathiazines and dioxazines were obtained from butylamine and ethanolamine. Under the chosen reaction conditions, ethylenediamine was converted into 5-[2-(perhydro-1,3,5-dithiazin-5-yl)ethyl]perhydro-1,3,5-dithiazine or substituted thiazetidine and oxazetidine, depending on the order of mixing of the starting reagents.