Synthesis of diethyl oxo phosphonates from monoterpene ketones – carvone, pinocarvone and 2-caren-4-one

Kolesnik, V. D.; Шакиров, М. М.; Ткачев, А. В.

doi:10.1070/mc1997v007n04abeh000764

Cited by 9 publications

(7 citation statements)

References 11 publications

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“…In the PMR-spectra ( Table 3 ) of derivatives 17 – 20 , the signals of protons of the guaiane skeleton and multiplets of protons H-11 (J P 11 H = 21–22), H-13a, and H-13b (J P 13 H = 18–20) were complicated by additional cleavage with the phosphorus nucleus by dialkyl phosphite groups. The values of SSCR JPH were in good agreement with the literature data [ 37 ]. Because of diastereotopic nature of alkoxy groups, due to the appearance of an additional chiral center at C-11, the signals of the methyl 17 and methylene groups 18 – 20 had different values of the chemical shift, and the splitting of these protons at the phosphorus nucleus led to an additional complication of these protons (the signals of protons at C-1’, C-1”, C-2’, C-2”, C-3’, C-3”, C-4’, and C-4” in Table 3 ).…”

Section: Resultssupporting

confidence: 89%

“…The presence of the 13 C–P bond follows from the data of 13 C NMR spectra. For example, for derivative 17 in the 13 C NMR spectrum, the signal of the C-13 nucleus was observed as a doublet with a large (of the order of 145.5 Hz) value of SSCC, which was in good agreement with the values of SSCC J CP from the literature [ 37 ]. Due to the influence of the 31 P nucleus of the dialkylphosphonate group in the 13 C NMR spectrum, additional cleavage of signals from other carbon nuclei was also observed.…”

Section: Resultssupporting

confidence: 78%

“…In continuation of the synthesis of estafiatin derivatives, interaction with dimethyl-, diethyl-, dipropyl-, and dibutylphosphites was considered under conditions similar to those described for monoterpene α-enones [ 37 ] and sesquiterpene lactone of the cadinane structure arteannuin B [ 36 ].…”

Section: Resultsmentioning

confidence: 99%

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Syntheses Based on 3,4α-Epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide

Адекенов¹

2022

Molecules

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The sesquiterpene γ-lactone estafiatin 1, the molecule of which has a structure of 3,4α-epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide, is characteristic of plants of the genera Achillea L. and Artemisia L. of the Asteraceae family. This article presents the results of chemical modification for three reaction centers of the estafiatin molecule 1: epoxy cycle, exomethylene group conjugated with γ-lactone carbonyl, and exomethylene group in position С10=С14; and at the same time 33 new derivatives were synthesized, the structures of which were established based on physicochemical constants, spectral data (IR-, PMR-, 13C-NMR), and X-ray diffraction analysis. The stereo- and regiospecificity, as well as the chemoselectivity of the reaction based on estafiatin molecule 1, are discussed. The reactivity of the substrate is significantly influenced by the stereochemistry of its molecule, the nature of the reagent, and the reaction medium. Based on the results of in silico screening, derivatives of estafiatin with high binding energies for both DNA-topoisomerase I and DNA-topoisomerase II were identified. The values of the inhibitory dose of IC50 for estafiatin 1 and its derivatives were determined on cell lines of eight types of tumors. In vivo experiments of the samples made it possible to establish that estafiatin 1 and its derivatives have pronounced antitumor activity against Pliss lymphosarcoma, Walker’s carcinosarcoma, sarcoma 45, sarcoma-180, alveolar liver cancer PC-1, leukemia P-388 and L-1210, and sarcoma-45 resistant to 5-fluorouracil.

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Section: Resultssupporting

confidence: 89%

Section: Resultssupporting

confidence: 78%

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Syntheses Based on 3,4α-Epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide

Адекенов¹

2022

Molecules

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“…589 Conjugate addition of the sodium salt of diethyl phosphite to the carenone 495 leads to the β-ketophosphonate 496. 590 (ϩ)-Car-3-ene 482 encapsulated in β-cyclodextrin is metabolised by Acetobacter aceti to a mixture of 8-hydroxy-m-cymene 497, cis-2-hydroxycar-3-en-5-one 498 and the keto-acid 499, amongst other products. 591 The presence of the β-cyclodextrin enhanced the stabilities of some of the products.…”

Section: Caranesmentioning

confidence: 99%

Monoterpenoids (mid-1997 to mid-1999)

Grayson

2000

Nat. Prod. Rep.

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In situ RNA hybridization and immunocytochemistry were used to establish the cellular distribution of monoterpenoid indole alkaloid biosynthesis in Madagascar periwinkle (Catharanthus roseus). Tryptophan decarboxylase (TDC) and strictosidine synthase (STR1), which are involved in the biosynthesis of the central intermediate strictosidine, and desacetoxyvindoline 4-hydroxylase (D4H) and deacetylvindoline 4-O-acetyltransferase (DAT), which are involved in the terminal steps of vindoline biosynthesis, were localized. tdc and str1 mRNAs were present in the epidermis of stems, leaves, and flower buds, whereas they appeared in most protoderm and cortical cells around the apical meristem of root tips. In marked contrast, d4h and dat mRNAs were associated with the laticifer and idioblast cells of leaves, stems, and flower buds. Immunocytochemical localization for TDC, D4H, and DAT proteins confirmed the differential localiza-tion of early and late stages of vindoline biosynthesis. Therefore, we concluded that the elaboration of the major leaf al-kaloids involves the participation of at least two cell types and requires the intercellular translocation of a pathway intermediate. A basipetal gradient of expression in maturing leaves also was shown for all four genes by in situ RNA hy-bridization studies and by complementary studies with dissected leaves, suggesting that expression of the vindoline pathway occurs transiently during early leaf development. These results partially explain why attempts to produce vin-doline by cell culture technology have failed. INTRODUCTION The organs forming the plant body consist of several different cell types that are organized in relation to each other and that confer specific functions to the resulting organ. Each cell type emerges from an undifferentiated meristem according to a sophisticated and partially understood developmental program (Sylvester et al., 1996; von Arnim and Deng, 1996). The commitment to differentiate into specialized structures involves the perception by cells in the meristem of a complex array of signals, which communicate cellular age, position in relation to other cells, and hormonal balance. Environmental factors, such as light and temperature, also play a critical role in modulating these signals throughout the process of organogenesis (Bernier, 1988; Dale, 1988; Sylvester et al., 1996). In addition to morphogenesis, developmental processes result in biochemical specialization of cells for the biosyn-thesis and/or accumulation of secondary metabolites, such as phenylpropanoids (Ibrahim et al.

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“…For instance, (1 S ,3 S ,4 R )-3,4-epoxycarane ( 11 ) and various hydroxylated limonene derivatives were employed as the starting materials in the synthesis of cannabinoids [ 14 ], and (1 S )-3-caren-5-one ( 14 ) was utilized in the synthesis of (diphenylphosphinophenyl)pyridine ligands used for the asymmetric synthesis as transition metal complexes [ 15 ], and in the synthesis of pyrethroids [ 16 ]. (1 S )-2-Caren-4-one ( 5 ) was utilized in the total synthesis of chiral oxophosphonates which can be employed in enantioselective catalysis [ 17 ]. While some of our products are easily obtained by common organic syntheses [(1 S ,3 S ,4 R )-3,4-epoxycarane ( 11 ), (1 R ,4 R )- p -menth-2-en-1,8-diol ( 6 )], the synthesis of others is complicated and time-consuming [(1 S )-2-caren-4-one ( 5 ), (1 S )-3-caren-2-one ( 9 ), (1 S )-3-caren-5-one ( 14 ), (1 R )- p -menth-2-en-7,8-diol ( 7 )].…”

Section: Resultsmentioning

confidence: 99%

Biotransformation of (1S)-2-Carene and (1S)-3-Carene by Picea abies Suspension Culture

et al. 2011

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Biotransformation of (1S)-2-carene and (1S)-3-carene by Picea abies suspension culture led to the formation of oxygenated products. (1S)-2-Carene was transformed slowly and the final product was identified as (1S)-2-caren-4-one. On the other hand, the transformation of (1S)-3-carene was rapid and finally led to the formation of (1S)-3-caren-5-one and (1S)-2-caren-4-one as equally abundant major products. The time-course of the reaction indicates that some products abundant at the beginning of the reaction (e.g. (1S,3S,4R)-3,4-epoxycarane and (1R)-p-mentha-1(7),2-dien-8-ol) were consumed by a subsequent transformations. Thus, a precise selection of the biotransformation time may be used for a production of specific compounds.

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Synthesis of diethyl oxo phosphonates from monoterpene ketones – carvone, pinocarvone and 2-caren-4-one

Cited by 9 publications

References 11 publications

Syntheses Based on 3,4α-Epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide

Syntheses Based on 3,4α-Epoxy-1,5,7α,6β(H)-guai-10(14),11(13)-dien-6,12-olide

Monoterpenoids (mid-1997 to mid-1999)

Biotransformation of (1S)-2-Carene and (1S)-3-Carene by Picea abies Suspension Culture

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