Our novel synthetic route to isoellipticine featured palladium‐catalyzed intramolecular reactions for the construction of the B ring of the pyridocarbazole nucleus. The adequate palladium‐catalyzed reaction depended upon the oxidation conditions that were applied in order to prepare the immediate synthetic precursor. When CAN was used to make the quinone intermediate, an oxidative cyclization through a double C−H bond activation was applied. Conversely, when the oxidation condition involved TCCA as oxidant, a direct C−H arylation was employed. Both approaches showed similar efficiencies in order to construct the pyridocarbazole nucleus. Isoellipticine was prepared in only 5 steps with a 21%–23% overall yield.
Ocimum gratissimum oil is used for various medicinal, food and cosmetic applications due to its high chemical variability. Local businesses have considered the economic exploitation of this plant. A specimen sampled at São Luís, MA, Brazil, with thymol and derivatives oil, was subjected to seasonal and circadian study, and to antifungal and antioxidant assays. It was possible to observe that the weather conditions showed a direct influence on the oil yield and variation of its constituents, mainly oxygenated monoterpenes and monoterpene hydrocarbons, with the predominance of thymol, γ-terpinene, and p-cymene. Principal component analysis (PCA) was able to justify the oil chemical variability of the seasonal (70%) and circadian (86%) study. Oil displayed inhibition for the fungus Corynespora cassiicola at a concentration above 0.3 µL mL-1 , and it showed a more significant activity by comparison to thymol. Using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay, the oil antioxidant activity was about 75% of thymol.
Ellipticine was synthesized in six steps and 20% global yield starting from the readily available 2,5-dimethoxy isoquinoline. Unprecedented regioselective control of the nucleophilic attack on the isoquinoline-5,8-dione is first described. Investigation of the possible pathways of this transformation through density functional theory calculations reveals unexpected N-oxide assistance in cascade tautomerizations, which was crucial for directing the nucleophilic attack and hastening the overall process. Using this strategy, we prepared the aniline-isoquinolinedione adduct and submitted it to an intramolecular double C−H cross-coupling activation to furnish ellipticinequinone, which gave ellipticine after a MeLi addition/BH 3 reduction sequence.
The tick Rhipicephalus microplus affects cattle health, with production loss in tropical and subtropical regions. Moreover, the use of commercial acaricides has been reduced due to the resistance of this parasite. Although alternatives such as plant bioactive molecules have been sought, essential oils present variations in their chemical constituents due to environmental factors, which can interfere with their acaricidal activity. The objective of the present study was to evaluate the seasonal influence of the essential oil of Ocimum gratissimum and its major constituents on acaricidal activity against R. microplus larvae. A high-yield essential oil of O. gratissimum and its major constituents were used, and a plant with a thymol-type oil was selected for seasonal analysis and acaricidal activity against R. microplus. Gas chromatography (GC) and GC-mass spectrometry (MS) were employed to identify 31 oil constituents (average yield of 6.26%). The main compounds were found to be thymol (33.4 to 47.9%), γ-terpinene (26.2 to 36.8%), and p-cymene (4.3 to 17.0%). Concerning acaricidal activity, the December (LC 0.84 mg/mL) and September (LC 1.58 mg/mL) oils obtained in the dry season were the most active, and assays performed with commercial standards revealed LC values of p-cymene, thymol, and γ-terpinene of 1.41, 1.81, and 3.08 mg/mL, respectively. Overall, lower acaricidal activities were found for oils produced from plants harvested in the rainy season. The results showed that seasonal variation in the chemical composition of the O. gratissimum essential oil influences its acaricidal activity. The seasonal variations in the thymol-type essential oil of O. gratissimum can represent an important strategy for the control of R. microplus.
Foi desenvolvido uma rota para síntese total da elipticina através de uma reação de ciclização intramolecular envolvendo ativação C-H catalisada por paládio. O método envolve a formação de uma isoquinolinodiona a partir de 2,5-dimetoxibenzaldeído seguido de uma reação de adição nucleofílica regiosseletiva da anilina.
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