Chemiluminescence from the biomimetic reaction of 1,2,4-trioxolanes and 1,2,4,5-tetroxanes with ferrous ions

Казаков, Д. В.; Timerbaev, Andrei R.; Safarov, F. E.; Nazirov, T. I.; Казакова, О. Б.; Ishmuratov, G. Yu.; Terent’ev, Alexander O.; Borisov, Dmitry; Tolstikov, A. G.; Толстиков, Г. А.; Adam, Waldemar

doi:10.1039/c1ra00784j

Cited by 15 publications

(9 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This work continues our studies on the synthesis and experimental examination of derivatives of plant terpenoids [18][19][20][21][22][23][24][25][26]. Considering that triterpene imi dazolides offer promise as potential antitumor agents, we describe here the synthesis and the results of the assessment of the antineoplastic activity of novel lupane imidazolides.…”

Section: Introductionmentioning

confidence: 96%

Synthesis and the antineoplastic activity of imidazolides of betulonic acid

et al. 2015

Self Cite

View full text Add to dashboard Cite

Synthesis of lupane C28-imidazolides, contained 3-oxo-, 3-oximino- and 2-cyano-2,3-seco-4(23)-en-frag ments in cycle A was carried out. The most antitumor activity at. in vitro testing showed 3-oximino-lup- 20(29)-en-28-yl-1H-imidazole-1-carboxylate; which inhibited the growth or induced apoptosis of non-small lung cancer, colon cancer, breast cancer, CNS cancer, ovarian cancer, prostate cancer, leucosis, melanoma cells. In experiments in mice its moderate antitumor activity against grafted breast adenocarcinoma Ca 755 and adenocarcinima of colon was observed.

show abstract

Section: Introductionmentioning

confidence: 96%

Synthesis and the antineoplastic activity of imidazolides of betulonic acid

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…We found earlier that oleanolic acid methyl ester was oxidized by ozone to methyl 12-oxoolean-28-oate [23] whereas oxidation of the analogous ursolic acid derivative gave 12-oxo-11S,13R-oxetane on ring C [24]. Limitations of methods for synthesizing such chiral non-racemic oxetanes were noted [25].Considering the aforementioned examples and continuing research on oxidative transformations of plant terpenoids [11,12,14,17,18,[26][27][28], we decided to determine the direction of the oxidation by ozone of 2-cyano-3,4-seco-4(23)-ene ursolic acid methyl ester (1) and to compare the results with those published for oxidation of the analogous oleanolic acid derivative [23].Oxidation of 1 with two unsaturated bonds in the C-4(23) (ring A) and C-12(13) (ring C) positions by ozone in CH 2 Cl 2 formed the three 2-cyano-3,4-seco-4-oxo derivatives 12-oxours-11S,13R-oxetane (2, 68%), 11-oxours-12-ene (3, 12%), and 12-hydroxy-4,11-dioxours-12-ene (4, 8%) (Scheme 1). Thus, oxidation of methyl 2-cyano-3,4-seco-4(23)-ene ursolate by ozone was non-selective, in contrast with the oxidation of the analogous oleanolic acid derivative, which enabled selective transformations of rings A and C to be carried out [23].…”

mentioning

confidence: 92%

“…Considering the aforementioned examples and continuing research on oxidative transformations of plant terpenoids [11,12,14,17,18,[26][27][28], we decided to determine the direction of the oxidation by ozone of 2-cyano-3,4-seco-4(23)-ene ursolic acid methyl ester (1) and to compare the results with those published for oxidation of the analogous oleanolic acid derivative [23].…”

mentioning

confidence: 98%

Oxidation of Methyl 2-Cyano-3,4-seco-4(23)-Ene-Ursolate by Ozone

et al. 2014

Self Cite

View full text Add to dashboard Cite

oxetane. The last was formed by oxidation of intermediate 12-oxoursolate. Ozonolysis of the ursolic acid derivative with two unsaturated bonds in the C-4(23) and C-12(13) positions was non-selective, in contrast with that reported previously for an analogous oleanolic-acid derivative.The triterpenoids oleanolic and ursolic acids are widespread in the plant world and exhibit various biological activities including antidiabetic, anticancer, antiviral, etc. [1][2][3]. Oxygenation of ring C is an important technique for modifying their structures in order to prepare new biologically active compounds. Examples include the synthesis from oleanolic acid of bardoxolone methyl (2-cyano-3,12-dioxooleane-1(2),9(11)-dien-28-oic acid methyl ester), which passed phase I clinical trials for treating cancer and phase II for treating chronic kidney disease in type 2 diabetes patients [4]. 3E,12D-Dihydroxyoleane-13E,28-lactone is a key intermediate in the synthesis of endothelin A receptor antagonists and a promising antidiabetic agent [5]. 12E-Hydroxyurs-11-ene-13E,28-lactone was produced by oxidative transformation of ursolic acid by ruthenium porphyrins and was active against A431 human skin cancer cells [5,6].The structures of the starting substrates are known to affect considerably the oxidation of triterpenoids [7][8][9][10][11][12][13][14][15][16][17][18][19][20]. For example, the reactivities of oleanolic and ursolic acid derivatives were found to differ during oxidation by dimethyldioxirane although these triterpenoids differ only by the location of the methyl in ring E [21]. Proposed schemes for separating mixtures of ursolic and oleanolic acids, which occur together in natural sources, were based on the inertness of the C-12(13) unsaturated bond of the former to the action of m-CPBA and HCOOH/H 2 O 2 [21,22]. We found earlier that oleanolic acid methyl ester was oxidized by ozone to methyl 12-oxoolean-28-oate [23] whereas oxidation of the analogous ursolic acid derivative gave 12-oxo-11S,13R-oxetane on ring C [24]. Limitations of methods for synthesizing such chiral non-racemic oxetanes were noted [25].Considering the aforementioned examples and continuing research on oxidative transformations of plant terpenoids [11,12,14,17,18,[26][27][28], we decided to determine the direction of the oxidation by ozone of 2-cyano-3,4-seco-4(23)-ene ursolic acid methyl ester (1) and to compare the results with those published for oxidation of the analogous oleanolic acid derivative [23].Oxidation of 1 with two unsaturated bonds in the C-4(23) (ring A) and C-12(13) (ring C) positions by ozone in CH 2 Cl 2 formed the three 2-cyano-3,4-seco-4-oxo derivatives 12-oxours-11S,13R-oxetane (2, 68%), 11-oxours-12-ene (3, 12%), and 12-hydroxy-4,11-dioxours-12-ene (4, 8%) (Scheme 1). Thus, oxidation of methyl 2-cyano-3,4-seco-4(23)-ene ursolate by ozone was non-selective, in contrast with the oxidation of the analogous oleanolic acid derivative, which enabled selective transformations of rings A and C to be carried out [23].

show abstract

“…As a part of our investigation program of the plant triterpenoids pharmacological potency (Kazakova et al 2010a, b;Kazakov et al, 2011;Kazakova et al 2011a, d;Kazakov et al, 2012;Kazakova et al 2013;Smirnova et al 2014Smirnova et al , 2015Tret'yakova et al, 2014;Yamansarov et al, 2015), we present here the synthesis of triterpenoids bearing cyanoethyl and aminopropoxy chains at the C-28 and C-3 or C-28 positions and their in vitro and in vivo anticancer activity. Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and anticancer activity of aminopropoxytriterpenoids

et al. 2015

View full text Add to dashboard Cite

Triterpenoids with aminopropoxy groups in C-28 or C-3 and C-28 positions were synthesized from betulin, erythrodiol, uvaol, oleantriol and betulinic acid Nmethylpiperazinylamide by cyanoethylation and the following catalytic hydrogenolysis. Computational estimating activity spectra of the designed compounds pointed out on their probable antineoplastic and proapoptotic activities. Their in vitro cytotoxic activity was evaluated at the National Cancer Institute, USA. Aminopropoxy derivatives of betulin, erythrodiol and oleantriol demonstrated the highest cytotoxic activity toward the most of 60 used tumor cell lines. Bisaminopropoxyerythrodiol revealed in vivo significant antineoplastic activity toward five mouse solid transplantable tumors. The results of in silico investigations and the efficacy of compounds in a broad panel of cell lines in vitro and the activity of bisaminopropoxyerythrodiol on the in vivo tumor models strongly suggest aminopropoxytriterpenoids as promising compounds for further investigation as anticancer agents. Graphical Abstract

show abstract

Chemiluminescence from the biomimetic reaction of 1,2,4-trioxolanes and 1,2,4,5-tetroxanes with ferrous ions

Cited by 15 publications

References 30 publications

Synthesis and the antineoplastic activity of imidazolides of betulonic acid

Synthesis and the antineoplastic activity of imidazolides of betulonic acid

Oxidation of Methyl 2-Cyano-3,4-seco-4(23)-Ene-Ursolate by Ozone

Synthesis and anticancer activity of aminopropoxytriterpenoids

Contact Info

Product

Resources

About