Isosteviol and some of its derivatives as receptors and carriers of amino acid picrates

Катаев, В. Е.; Strobykina, I. Yu.; Militsina, O. I.; Korochkina, M. G.; Федорова, О. В.; Овчинникова, И. Г.; Валова, М. С.; Русинов, Г. Л.

doi:10.1016/j.tetlet.2006.01.126

Cited by 14 publications

(7 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Upon activation of the carboxylic acid of (–)‐isosteviol as the acid chloride and subsequent reaction with, for example, diols,65 dibromoalkanes,66 or diamines, tweezer‐like structure 74 can be obtained 67,68. These diamide structures have proven to be potent receptors and carriers of amino acid picrates based on phenylalanine and tryptophan through a liquid chloroform phase,67 partly exhibiting better extraction ability than dibenzo‐18‐crown‐6. In addition to the methylene or amide spacers depicted in Figure 7, azine and hydrazide linkers69 (showing high tuberculostatic activity) as well as aliphatic amide linkers67,68 have been reported.…”

Section: Applicationsmentioning

confidence: 99%

“…These diamide structures have proven to be potent receptors and carriers of amino acid picrates based on phenylalanine and tryptophan through a liquid chloroform phase,67 partly exhibiting better extraction ability than dibenzo‐18‐crown‐6. In addition to the methylene or amide spacers depicted in Figure 7, azine and hydrazide linkers69 (showing high tuberculostatic activity) as well as aliphatic amide linkers67,68 have been reported. Moreover, the anhydride of (–)‐isosteviol can be obtained by treating (–)‐isosteviol with isostevioyl chloride 33…”

Section: Applicationsmentioning

confidence: 99%

See 1 more Smart Citation

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

2013

View full text Add to dashboard Cite

(–)‐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.

show abstract

Section: Applicationsmentioning

confidence: 99%

Section: Applicationsmentioning

confidence: 99%

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

2013

View full text Add to dashboard Cite

show abstract

“…As a building block, an optically pure keto carboxylic acid with a concave arrangement of these functional groups is required. [13][14][15] Apart from their cytotoxic activities, compounds based on (-)-isosteviol have found application in various fields of synthetic chemistry, for example as carriers for amino acid picrates by forming tweezer-like receptor structures, [16] as chiral catalysts in aldol reactions, [17] or in the complexation of aromatic compounds. In this context, the nat-urally occurring diterpene (-)-isosteviol 1 (Figure 1) [10] seems to provide all the required molecular entities in suitable positions.…”

Section: Introductionmentioning

confidence: 99%

Derivatives of (–)‐Isosteviol with Expanded Ring D and Various Oxygen Functionalities

2012

View full text Add to dashboard Cite

(–)‐Isosteviol is a unique ex‐chiral‐pool building block that is readily available. Both functional groups are aligned in a concave manner. The methyl moiety on the backbone also points in this direction, creating a strong asymmetric environment close to these functional groups. The slightly divergent orientation of the keto and carboxy functions limits its use in the construction of supramolecular architectures as optically pure divalent building blocks. By selective transformations, ring D of (–)‐isosteviol can be expanded and equipped with oxygen‐containing functionalities, providing a variety of useful and rigid building blocks with defined stereochemistry.

show abstract

“…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.…”

mentioning

confidence: 99%

“…For example, the ketone of the isosteviol moiety was reacted to produce several imine derivatives (12)(13)(14) (Scheme 1), the PMR spectra of which had resonances for the isosteviol and chlorin portions that were analogous to those of these same portions in the spectrum of the starting chlorin conjugate with isosteviol (5). Furthermore, PMR spectra of the resulting imine derivatives of isosteviolchlorins showed resonances for hydroxyl (for 12, 2.19 ppm, 1H, br.s, OH-16′), methoxyl (for 13, 3.76 ppm, 3H, s, CH 3 O-21′), and thiosemicarbazone (for 14, 8.23 ppm, 1H, br.s, NH-16′).…”

mentioning

confidence: 99%

Synthesis of conjugates based on chlorin and isosteviol building blocks

et al. 2009

View full text Add to dashboard Cite

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...

show abstract

Isosteviol and some of its derivatives as receptors and carriers of amino acid picrates

Cited by 14 publications

References 14 publications

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

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

Derivatives of (–)‐Isosteviol with Expanded Ring D and Various Oxygen Functionalities

Synthesis of conjugates based on chlorin and isosteviol building blocks

Contact Info

Product

Resources

About