Diesters on the basis of 16-hydroxyisosteviol and dicarboxylic acids as carriers of Fe(III) picrates

Катаев, В. Е.; Militsina, O. I.; Strobykina, I. Yu.; Gubaidullin, А. Т.; Зверев, В. В.; Kataeva, О. N.; Федорова, О. В.; Валова, М. С.; Русинов, Г. Л.

doi:10.1007/s10847-007-9351-y

Cited by 10 publications

(11 citation statements)

References 23 publications

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“…On the contrary, when n = 6, diacid molecules have completely unfolded structure of 3b kind (Figure 3) in which isosteviol moieties were moved far apart. [10] It was evident for us that a reaction of both diacid having tweezer-like structure 3a and diacid having unfolded (2) 293 (2) 296 (2) 296 (2) Space group C2 P212121 P1 P212121 V.E. Kataev et al structure 3b (Figure 3) with a binucleophile having a length which agrees closely with the distance between the COOH groups of diacids should afford binuclear macrocycles of 2c kind ( Figure 2).…”

Section: Resultsmentioning

confidence: 79%

“…The reason is that molecular structures of diacids 3 depend on the length of diester linker bonding two isosteviol fragments (Figure 3). According to the X-ray data, [10] when n = 1 (or 4), diacid molecules have completely folded tweezer-like structure of 3a kind (Figure 3) with one isosteviol moiety overhanging another. On the contrary, when n = 6, diacid molecules have completely unfolded structure of 3b kind (Figure 3) in which isosteviol moieties were moved far apart.…”

Section: Resultsmentioning

confidence: 99%

“…We also were sure that a reaction of diacid having unfolded structure 3b (Figure 3) with a binucleophile having the length which is much less than the distance between the COOH groups of diacid should lead exclusively to a tetranuclear macrocycle of 2d kind ( Figure 2). To examine this hypothesis we carried out the reactions of diacid 5 [9] which, according to X-ray data, [10] has unfolded structure 3b with ditosylates of 1,8-n-octanediol, 1,6-nhexanediol, and ethylene glycol (Scheme 1). To obtain diacid 5, firstly isosteviol 1 was converted to the dihydroisosteviol 4 by the reaction with NaBH 4 in CH 3 OH, [8] and compound 4 was obtained in the form of 16(R)-epimer as in many other cases.…”

Section: Resultsmentioning

confidence: 99%

“…Tetranuclear macrocycles were formed in low yields just in the reaction of diacid 5 with 1,6-n-hexanediol ditosylate that afforded the macrocycle 11 in 7 % yield, and in the reaction of diacid 5 with ethylene glycol ditosylate that afforded the macrocycle 19 (n = 6) 20 (n = 8) Macrocycles on the Basis of Diterpenoid 12 in 6 % yield. The fact that the reaction of diacid 5 having unfolded structure of 3b kind [10] (Figure 3) with ethylene glycol ditosylate possessing the length that is much less than the distance between the COOH groups of diacid 5 provided mainly the binuclear macrocycle 9, rather than tetranuclear macrocycle 12 was perfectly incomprehensible. This raised the question: perhaps the reason was that the structure of diacid 5 is not unfolded enough?…”

Section: Resultsmentioning

confidence: 99%

“…The mixture was refluxed for 26 h. After removing the solvent under reduced pressure, a precipitate was purified using chromatography. 2,11,14,12(16,10,13, 2,11,14,12(16,10,13, 2,11,14,12(16,10,13, 2,11,14,23,26,35,38,12,25,36(16, cyclooctatetracontaphane-3,10,13,24,27,34, 37,48-octaone (10 2,11,14,21,24,33,36,12,23,34(16, cyclotetratetracontaphane-3,10,13,22, 25,32,35,44-octaone (11 2,11,14,17,20,29,32,12,19,30(16, cyclohexatriacontaphane-3,10,13,18,21, 28,31,36-octaone (12 2,13,16,14(16,…”

Section: Synthesesmentioning

confidence: 99%

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Novel Macrocyclic Derivatives of Diterpenoid Isosteviol

Andreeva¹,

Strobykina²,

Kataeva³

et al. 2013

MHC

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Section: Resultsmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Synthesesmentioning

confidence: 99%

See 3 more Smart Citations

Novel Macrocyclic Derivatives of Diterpenoid Isosteviol

Andreeva¹,

Strobykina²,

Kataeva³

et al. 2013

MHC

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(–)‐Isosteviol as a Versatile Ex‐Chiral‐Pool Building Block for Organic Chemistry

2013

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(–)‐Isosteviol is readily available in large quantities by the acidic treatment of a common alternative sweetener. The two functional groups of (–)‐isosteviol are presented on the same side of the ent‐beyerane scaffold with a mutual C–C distance of about 7 Å. Their unique concave arrangement experiences a strong asymmetric environment due to an adjacent methyl group. Consequently, this building block has found several applications in supramolecular chemistry and organocatalysis. These areas and the chemical modification of this scaffold as well as its biological activity are surveyed.

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Synthesis of conjugates based on chlorin and isosteviol building blocks

et al. 2009

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Conjugates containing ent-beyerane carbocyclic frameworks on the periphery of a porphyrin macrocycle were prepared by acylation of chlorin e 6 derivatives with hydroxyl and amino groups using ent-16-ketobeyeran-19-oic acid chloride (diterpenoid isosteviol).Chlorophyll a derivatives such as chlorin e 6 amides and pyropheophorbide a in addition to many others are currently being investigated as photosensitizers for photodynamic therapy of oncological and viral diseases. Several of them are the active ingredients in preparations that are already used in clinical practice [1]. We have used the diterpenoid isosteviol (ent-16-ketobeyeran-19-oic acid, 1), which exhibits various types of physiological activity (hypotensive and antihypertensive effects [2], inhibition of oxidative phosphorylation [3], reduction of ATP-activity of certain phosphotases and oxidases [4]), to modify amino-and hydroxychlorins. The biological activity of isosteviol and its derivatives is due mainly to their interaction with cell membranes [2][3][4]. Model experiments showed that certain isosteviol derivatives can facilitate the transport of amino acids through membranes [5,6]. Thus, it can be surmised that introducing onto the periphery of the chlorin macrocycle an isosteviol moiety, which is a functionalized ent-beyerane carbocyclic diterpenoid framework, will facilitate better interaction of the synthesized conjugate with cell membranes. This will increase the photosensitizing effect and could result in the preparation of new biologically active compounds.We used an acylation reaction to introduce the ent-beyerane carbocyclic framework onto the periphery of the chlorin ring. The acylating agent was isosteviol acid chloride (2), which was prepared using thioyl chloride and isosteviol (1) [7] (Scheme 1). Amino and hydroxy groups that were convenient for acylation were introduced onto the periphery of the chlorin macrocycle using opening of the exocycle of methylpheophorbide a (3) [8-11] to synthesize amino-and hydroxychlorins (4-6). Opening of the exocycle by ethylenediamine in combination with amidation of the ester substituent in the 17-position by the same diamine produced a chlorin (10) with two amino groups [12].Hydroxy and amino groups of the chlorins (4-6 and 10) were acylated by isosteviol acid chloride (2) by refluxing in THF in the presence of an excess of triethylamine (Scheme 1). PMR spectra of all three compounds (6-8) showed resonances at strong field for protons of the isosteviol moiety, in particular 3H singlets for methyls. Furthermore, PMR spectra of 7 and 8 exhibited an additional broad triplet for the amide that was formed by acylation of the amine by 2. Using diaminochlorin 10 as the substrate for the acylation and a two-fold molar excess of 2 produced in 30% yield a chlorin with two diterpenoid moieties (11) (Scheme 1). PMR spectra of 11 had two additional broad triplets of amides that were formed by acylation of diaminochlorin with 2 when compared with the spectrum of starting 10. Furthermore, a doubled set of singlets fo...

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Diesters on the basis of 16-hydroxyisosteviol and dicarboxylic acids as carriers of Fe(III) picrates

Cited by 10 publications

References 23 publications

Novel Macrocyclic Derivatives of Diterpenoid Isosteviol

Novel Macrocyclic Derivatives of Diterpenoid Isosteviol

(–)‐Isosteviol as a Versatile Ex‐Chiral‐Pool Building Block for Organic Chemistry

Synthesis of conjugates based on chlorin and isosteviol building blocks

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