A new strategy for the alpha-vinylation of ketones: Application to an enantioselective synthesis of sesquiterpene (+)-alpha-elemene

A new, simple and preparatively useful protocol for the construction of a-vinyl ketones, particularly those bearing a quaternary carbon centre, from the corresponding alkenes has been devised. Our four-step strategy consists of dichloroketene addition, base catalysed ring contraction to 'push-pull' cyclopropane esters, reduction and eliminative cyclopropane fragmentation to unravel the a-vinyl ketone moiety. The generality of this approach has been demonstrated with a few representative olefins and good regio- and stereocontrol has been observed. As an application of this methodology, an enantioselective synthesis of sesquiterpene hydrocarbon (+)-alpha-elemene (42) from R-(+)-limonene (43) has been accomplished.

Flavour characterization of fresh and processed pennywort (Centella asiatica L.) juices

The flavour characteristics of fresh and processed pennywort juices treated by pasteurization, sterilization and high pressure processing (HPP) were investigated by using solid-phase micro-extraction combined with gas chromatography-mass spectrometry. Sesquiterpene hydrocarbons comprised the major class of volatile components present and the juices had a characteristic smell due to the presence of volatile compounds including β-caryophyllene, humulene, E-β-farnesene, α-copaene, alloaromadendrene and β-elemene. All processing operations caused a reduction in the total volatile concentration, but HPP caused more volatile acyclic alcohols, aldehydes and oxygenated monoterpenoids to be retained than pasteurization and sterilization. Ketones were not present in fresh pennywort juice, but 2-butanone and 3-nonen-2-one were generated in all processed juices, and 2-nonanone and 2-hexanone were present in pasteurized and sterilized juices. Other chemical changes including isomerization were also reduced by HPP compared to pasteurization, and sterilization.

COMPOSITION OF SUPERCRITICAL CARBON DIOXIDE EXTRACTS OF PITANGA (EUGENIA UNIFLORA L.) LEAVES

The leaves of the Pitanga bush (Eugenia uniflora L.) are considered to be effective against many diseases. Extracts from Pitanga leaves have been found to show pronounced anti-inflammatory action and to have antimicrobial and antifungal activities, among other properties. In this work, extracts from Pitanga leaves were obtained by hydrodistillation and by extraction with supercritical carbon dioxide (SC-CO(2)) at three conditions of temperature and pressure. In the SC-CO(2) extractions also were collected the components that are lost with the CO(2) in the exit of the system using Porapak-Q polymer trap. All extracts were analyzed by gas chromatography-mass spectrometry (GC-MS). Thirty-nine compounds were found in the extracts and twenty-six were identified. The main components identified in the extracts in decreasing quantitative order were: curzerene, germacrene B, C(15)H(20)O(2) and beta-elemene for hydrodistillation; C(15)H(20)O(2) and curzerene for SC-CO(2) extracts and 3-hexen-1-ol, curzerene, C(15)H(20)O(2), beta-elemene and germacrene B for SC-CO(2) extracts captured in Porapak-Q. PRACTICAL APPLICATIONS The natural extracts are a potential source of compounds possessing biological activities. They can be used in foods, pharmaceutics and cosmetics. Pitanga is an exotic fruit from Brazil and extracts from its leaves have been used against many diseases in Brazilian folk medicine. Supercritical extraction is an interesting process for the production of natural extracts because it is a clean process and the knowledge of composition of extracts is crucial for the identification of the probable active components.

Chemical Composition and Antimicrobial Activity of the Essential Oil from Rollinia sericea (REFr.) REFr. (Annonaceae) Leaves

The chemical composition of the essential oil of Rollinia sericea (R.E.Fr.) R.E.Fr. leaves was determined by GC and GC/MS analysis. The analysis revealed the presence mainly of sesquiterpenes: beta-elemene (10%), beta-caryophyllene (10.0%), bicyclogermacrene (9.1%), germacrene-D (8.2%), bicycloelemene (6.2%) and (Z)-nerolidol (5.3%). Rollinia sericea oil was able to inhibit the growth of both fungi Aspergillus niger (16404) and Candida albicans (ATCC 10231) as well as the Gram-positive bacterium Staphyloccocus aureus (ATCC 6538) but it was inactive against the Gram-negative bacteria Escherichia coli (ATCC 8739) and Pseudomonas aeruginosa (ATCC 9027).

Chemical Composition and Antimicrobial Activity of the Essential Oil from Croton heterocalyx Baill. (Euphorbiaceae s.s.) Leaves

The chemical composition and the antimicrobial activity of the essential oil from Croton heterocalyx leaves were evaluated. The oil which was analyzed by GC and GUMS was found to contain germacrene D (12.5%), bicyclogermacrene (11.2%), delta-elemene (9.2%) beta-elemene (8.2%), spathulenol (6.9%), linalool (5.4%) and 1,8-cineole (3.7%) its major components. Croton. heterocalyx oil displayed a high inhibitory activity against the fungi Aspergillus niger (16404) and Candida albicans (ATCC 10231.) as well its the Gram-positive bacterium Staphylococcus aureus (ATCC 6538), hut a very weak activity was observed for the Gram-negative bacteria Escherichia coli (ATCC 8739) and Pseudomonas aeruginosa (ATCC 9027).

Composição fitoquímica dos óleos essenciais de folhas de Lippia alba (Mill.)N.E.Br. em diferentes épocas de colheita e partes do ramo

This work aimed to determine the best harvest time for biomass production, yield and essential oil composition considering the seasonal variation (spring, summer, autumn and winter) on different plant parts (apical, medial and basal). Essential oils were extracted by hydro-distillation with a Clevenger apparatus for both fresh and dry mass obtained in field and lab conditions respectively. The extracted essential oils were analyzed by GS/MS (Shimadzu, QP-5000). The chemical components were identified by comparing their mass spectrum to the patterns filed in the MS computer memory (Wiley,139,Lib.), to the literature references, and by co-injection with authentic standards. Applying phyto-chemical tests on fresh and dry mass, the chemical component percentages of essential oils were calculated and identified as follows: citral (neral and geranial), myrcene, caryophylene and elemene.

Essential oil composition of Croton palanostigma Klotzsch from north Brazil

Os óleos essenciais das folhas, ramos finos, galhos, cascas do caule e frutos de Croton palanostigma foram analisados por CG e CG-EM. Os componentes principais determinados no óleo das folhas foram linalol (25,4%), (E)-cariofileno (21,0%), metileugenol (17,2%) e β-elemeno (6,0%); no óleo dos ramos finos foram α-pineno (41,4%), limoneno (29,0%), sabineno (11,5%) e β-pineno (5,7%); no óleo dos galhos foram metileugenol (24,1%), (E)-metilisoeugenol (15,3%), α-pineno (11,2%) e (E)-cariofileno (8,5%); no óleo das cascas do caule foram a-pineno (31,6%), metileugenol (25,6%) e (E)-metilisoeugenol (23,7%); e no óleo dos frutos foram linalol (42,7%), metileugenol (16,3%) e β-elemeno (6,4%). Análise estatística mostrou que as folhas e os frutos apresentam significante similaridade entre si, assim como os galhos e as cascas do caule. Adicionalmente, o óleo obtido das cascas do caule possui elevada atividade larvicida sobre Artemia salina (CL₅₀, 3,71 ± 0,01 mg mL^-1).

Chemical composition of essential oils from the vegetative and reproductive structures of Copaifera langsdorffii Desf

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

(+)-Germacrene A Biosynthesis : The Committed Step in the Biosynthesis of Bitter Sesquiterpene Lactones in Chicory

The leaves and especially the roots of chicory (Cichorium intybus L.) contain high concentrations of bitter sesquiterpene lactones such as the guianolides lactupicrin, lactucin, and 8-deoxylactucin. Eudesmanolides and germacranolides are present in smaller amounts. Their postulated biosynthesis through the mevalonate-farnesyl diphosphate-germacradiene pathway has now been confirmed by the isolation of a (+)-germacrene A synthase from chicory roots. This sesquiterpene cyclase was purified 200-fold using a combination of anion-exchange and dye-ligand chromatography. It has a Km value of 6.6 μm, an estimated molecular mass of 54 kD, and a (broad) pH optimum around 6.7. Germacrene A, the enzymatic product, proved to be much more stable than reported in literature. Its heat-induced Cope rearrangement into (−)-β-elemene was utilized to determine its absolute configuration on an enantioselective gas chromatography column. To our knowledge, until now in sesquiterpene biosynthesis, germacrene A has only been reported as an (postulated) enzyme-bound intermediate, which, instead of being released, is subjected to additional cyclization(s) by the same enzyme that generated it from farnesyl diphosphate. However, in chicory germacrene A is released from the sesquiterpene cyclase. Apparently, subsequent oxidations and/or glucosylation of the germacrane skeleton, together with a germacrene cyclase, determine whether guaiane- or eudesmane-type sesquiterpene lactones are produced.