Preparation, X-ray structural studies and plant growth regulatory activity of methyl 6alpha,7beta-thiocarbonyldioxyvouacapan-17 beta-oate

Rubinger, Mayura M. M.; Castelo-Branco, Pedro de A.; Guilardi, Silvana; Souza, Elysângela M. R.; Gambardella, Maria Teresa do Prado; Borges, Eduardo E.L.; Ferreira-Alves, Dalton L.; Piló‐Veloso, Dorila

doi:10.1590/s0103-50532004000200010

Cited by 10 publications

(8 citation statements)

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“…3,4 Some derivatives of 1 have been prepared for biological evaluation. 2,5,6 Here we report the preparation of the esters 4-9 (Scheme 1), and an evaluation of their phytotoxic properties.…”

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Synthesis and phytotoxicity evaluation of novel 6α,7β-dihydroxyvouacapan-17β-oic acid derivatives

Castelo-Branco

Rubinger

Resende

et al. 2006

Journal of Chemical Research

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The 6a,7b-dihydroxyvouacapan-17b-oic acid (1) isolated from Pterodon polygalaeflorus Benth has shown allelopathic and plant growth regulatory properties. Six novel esters of (1) were prepared and their effects on the radical growth of Sorghum bicolor L. and Cucumis sativus L. were evaluated.The natural product 6a,7b-dihydroxyvouacapan-17b-oic acid (1) and the lactone 2 (Scheme 1), exhibit anti-inflammatory, analgesic activities, 1 and allelopathic activity. 2 Several terpenoids are involved in plant allelopathic interactions but little is known about the effects of diterpenes on plant growth regulation. 3,4 Some derivatives of 1 have been prepared for biological evaluation. 2,5,6 Here we report the preparation of the esters 4-9 (Scheme 1), and an evaluation of their phytotoxic properties.The acid (1) was isolated from the P. polygalaeflorus Benth fruits. 7 The d-hydroxy-lactone 2 5 and d-keto-lactone 3 8 were prepared as shown in Scheme 1. The novel compounds 4-9 were prepared in good yields (77-89 %) using catalytic amounts of NaOH. The lactone 3 is not very soluble in the alcohols. Thence the end of the reaction could be observed by TLC and by the total disappearance of the solid phase.The esters 4-9 were characterised by elemental analysis, IR and NMR spectroscopy. The IR spectra of all the esters 4-9 showed a hydroxyl absorption between 3495 and 3465 cm -1 and strong C=O stretching bands in the 1735-1709 cm -1 range due to the ester and ketone groups. In the 13 C NMR spectra, the carbonyl signals were observed around d C 174 (ester) and d C 209 (ketone). The 1 H NMR signals due to the furanditerpene backbone hydrogens of the esters 4-9 are very similar to those observed in the spectrum of the parent lactone 3. 8 It is interesting to note the multiplicity of the signal at d H 1.70 in the 1 H NMR spectrum of 6 which is a sextet assigned to H-2', indicating non-resolvable coupling constants (J 7.3 Hz)with the theoretically non-equivalent hydrogens H-1' and H-3'. Other features worth mentioning are the nonequivalence of the H-1' methylenic hydrogens revealed by the double doublets observed in the 1 H NMR spectrum of compound 9 at d H 4.61 and 4.71 with Jgem 12.2 Hz and Jvic 7.2 Hz with H-2'. The remaining signals were in accordance with the proposed structures.It was previously reported that 1 at 100 ppm inhibited the root growth of Sorghum bicolor L. (30-40 %) and stimulated Cucumis sativus L. (5-10 %). 2 Recently it was shown that lactones 2 and 3 inhibited the uncoupled noncyclic electron transport and ATP synthesis, behaving as Hill reaction inhibitors, and the carbonyl at C-6 of 3 affected the photophosphorylation. 2,8 Compounds 1-9 were evaluated in vitro against S. bicolor and C. sativus using a different methodology. 9 As the compounds were not soluble in the usual formulations, 9 an aqueous solution of a triblock copolymer and DMSO was used instead. Table 1 shows the radical lengths. Under these conditions, the novel compounds and the parent lactones did not significantly affect the growth of S. bicolor.

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“…The acid (1) was isolated from the P. polygalaeflorus Benth fruits. 7 The d-hydroxy-lactone 2 5 and d-keto-lactone 3 8 were prepared as shown in Scheme 1. The novel compounds 4-9 were prepared in good yields (77-89 %) using catalytic amounts of NaOH.…”

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confidence: 99%

Synthesis and phytotoxicity evaluation of novel 6α,7β-dihydroxyvouacapan-17β-oic acid derivatives

Castelo-Branco

Rubinger

Resende

et al. 2006

Journal of Chemical Research

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“…Analgesic and anti-inflammatory activities have been observed for compound 1 [9][10][11]. The relationships between the chemical structure and the biologic activities of 1 and its derivative lactones [12][13][14][15], Mannich bases [15,16], amides [17][18][19], carbamates [20], and other compounds [21][22][23][24][25][26][27] have been investigated. These derivatives show anti-inflammatory, analgesic, sedative, anticonvulsant, and plant growth regulatory activities.…”

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confidence: 99%

Theoretical and experimental NMR studies of the Swern oxidation of methyl 6α,7β-dihydroxyvouacapan-17β-oate

et al. 2008

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This work describes the synthesis of new derivatives of 6a,7b-dihydroxyvouacapan-17b-oic acid (1) employing the Swern method for the oxidation of C-6 and C-7 of methyl 6a,7b-di-hydroxyvouacapan-17b-oate (2) and the formation of methyl 6,7-dioxovouacapan-17b-oate (3). NMR structural studies associated with theoretical calculations of reaction intermediates and products are also reported. The mixture of methyl 7b-hydroxy-6-oxovouacapan-17b-oate (4; 21%) and methyl 6a-hydroxy-7-oxovouacapan-17b-oate (5; 79%) was the product from the first step of the oxidation of 2. The lower energy of 5, calculated by HF/6-31G* and DFT/BLYP/6-31G* methods, reinforces the thermodynamic control proposed for the reaction. After further Swern oxidation of the mixture of 4 and 5, the isomeric form methyl 6-hydroxy-7-oxovouacap-5-en-17b-oate (6) was obtained. Theoretical calculations indicate a lower energy for the mono-enol 6 than the 1,2-diketo 3 and the other mono-enol methyl 7-hydroxy-6-oxovouacap-7-en-17b-oate (7).

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“…4). BELINELO et al, 2002;CAMPOS et al, 1994;CASTELO-BRANCO et al, 2008;DEMUNER et al, 1996;SANTOS et al, 2008;EUZÉBIO et al, 2009EUZÉBIO et al, , 2010FASCIO et al, 1976;GALCERAN et al, 2011;KING-DÍAZ et al, 2006a, 2006bMONTEIRO, 1973;OMENA et al, 2006;RUBINGER et al, 2004 6α,7β-diidroxivouacapan-17β-oato de metila (7 ARRIAGA et al, 2000;SANTOS et al, 2008;FASCIO et al, 1976;KING-DÍAZ et al, 2010;MONTEIRO, 1973;OMENA et al, 2006;RUBINGER et al, 2004;SPINDOLA et al, 2009SPINDOLA et al, , 2010SPINDOLA et al, , 2011 7βacetoxi-6α-hidroxivouacapan-17β-oato de metila (8)…”

Section: Biossíntese Dos Vouacapanosunclassified

“…Após o processo extrativo, o solvente é removido e o extrato é submetido à cromatografia em coluna para a obtenção dos vouacapanos (DEMUNER et al, 1996;FASCIO et al, 1976;MONTEIRO, 1973;PIMENTA et al, 2006;RUBINGER et al, 2004;SERVAT et al, 2012;SPINDOLA et al, 2009SPINDOLA et al, , 2010. Antes da purificação por coluna cromatográfica, pode ser realizado fracionamento pelo processo de extração por solvente (OMENA et al, 2006;VIEIRA et al, 2008) ou extração ácido-base (ARRIAGA et al, 2000;CAMPOS et al, 1994;FASCIO et al, 1976;MONTEIRO, 1973).…”

Section: Extraçãounclassified

Avaliação in vitro das atividades antimicrobiana e anti-inflamatória de vouacapanos de Pterodon emarginatus Vogel (FABACEAE)

Oliveira¹

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This research aimed to evaluate the antimicrobial and anti-inflammatory activities of Pterodon emarginatus Vogel (Fabaceae). The fruits were collected in the municipalities of Campestre and Bela Vista de Goiás (State of Goiás, Brazil). Diterpene vouacapanes were detected only in the oleoresin of the fruits of Bela Vista de Goiás, and so this sample was fractionated by partition. The dichloromethane: hexane fraction of this oleoresin was subjected to open column chromatography. Diaion HP-20 was the stationary phase and the mobile phase was acetonitrile: water with increasing elution force. An HPLC method was developed in order to monitor chromatographic fractionation. Subfractions 7-12 (Group 1) were pooled and subjected to reverse-phase semi-preparative HPLC separation. The antimicrobial activity of voucapans and Pterodon oleoresin was determined against 8 Gram-positive strains, 11 Gram-negative strains and 4 Candida species by plaque microdilution assay. Cytotoxicity was evaluated in HaCaT cells by the colorimetric method of MTT -[3-(4,5-dimethylthiazol-2-yl) -2,5diphenyltetrazolium bromide]]. The anti-inflammatory potential was determined by the following evaluations: phospholipase A2 inhibitory activity by fluorimetric method, expression of COX-2 and NRF2 and quantification of inflammatory cytokines IL-6 and IL-8 by flow cytometry. Samples were tested at concentrations which maintained 90% viability (CV90) of HaCaT cells, in order to avoid the use of cytotoxic concentrations in anti-inflammatory assays. Three compounds were identified via NMR: 6α, 19β-diacetoxy-7β, 14β-dihydroxyivouacapane (V1), 6α-acetoxy-7β, 14β-dihydroxyivouacapane (V2) and methyl α-acetoxy-7βhydroxyivacapan-17β-oate (V3). All three vouacapans and oleoresin were more active against Gram-positive strains. Regarding Gram-negative strains, the samples were only active against Pseudomonas aeruginosa. Vouacapane V2 showed the best antibacterial activity, proving to be active against 7 of the 8 Gram-positive bacteria evaluated, presenting values of minimum inhibitory concentration between 62.5 and 125 μg/mL. Samples had no inhibitory activity against the strains C. glabrata, C. kruzei, C. parapsilosis and C. albicans. The olororesin and V1, V2 and V3 had CV90 of 7.5 μg/mL, 19.0 μg/mL, 13.8 μg/mL and 4.00 μg/mL, respectively, against HaCaT cells. The Pterodon oleoresin and the V2 and V3 vouacapans inhibited phospholipase A2 activity by 30.78%, 24.96% and 77.64%, respectively. V2 and V3 vouacapans at CV90 inhibited COX-2 expression in 28.3% and 33.17%, respectively. Sucupira oleoresin was able to inhibit IL-6 production by 35.47%. The expression of NRF2 and the production of IL-8 were not altered by the substances tested, in comparison to the control. Results support the popular use of sucupira fruits as antibacterial and anti-inflammatory and show that these activities may be associated with the presence of vouacapans.

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Preparation, X-ray structural studies and plant growth regulatory activity of methyl 6alpha,7beta-thiocarbonyldioxyvouacapan-17 beta-oate

Cited by 10 publications

References 3 publications

Synthesis and phytotoxicity evaluation of novel 6α,7β-dihydroxyvouacapan-17β-oic acid derivatives

Synthesis and phytotoxicity evaluation of novel 6α,7β-dihydroxyvouacapan-17β-oic acid derivatives

Theoretical and experimental NMR studies of the Swern oxidation of methyl 6α,7β-dihydroxyvouacapan-17β-oate

Avaliação in vitro das atividades antimicrobiana e anti-inflamatória de vouacapanos de Pterodon emarginatus Vogel (FABACEAE)

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