Synthesis of racemic and chiral albicanol, albicanyl acetate and cyclozonarone: cytotoxic activity of ent-cyclozonarone

The total synthesis of racemic cyclozonarone ((±)-3) was achieved from E,E-farnesol (4) in an eight-step sequence in 6.6% overall yield. Albicanol ((±)-1) and its acetate ((±)-2) are intermediates. A similar sequence starting from natural (-)-drimenol (5) gave (+)-albicanol (1) and (+)-cyclozonarone (3) (42% and 11% yield, respectively). The cytotoxic activity of (+)-cyclozonarone was assayed and showed some selectivity towards MS-1 (mice endothelial cells).A síntese completa da mistura racêmica do cyclozonarone ((±)-3), foi obtida a partir do E,E-farnesol (4) em uma seqüência de oito passos com um rendimento geral de 6,6%. O albicanol ((±)-1) e seu acetato ((±)-2) são intermediários. Uma seqüência inicial, similar a partir do produto natural (-)-drimenol (5), produziu o(+)-albicanol (1) e o(+)-cyclozonarone (3) com 42% e 11%, respectivamente. A atividade citotóxica do composto(+)-cyclozonarone foi avaliada e mostrou alguma seletividade para MS-1 (células endoteliais de camundongos).Authors are grateful to Dirección de Investigación y Postgrado, Facultad de Química, Pontificia Universidad Católica de Chile, for financial support, to MECESUP grant UCH 0116 de la Red Nacional de Doctorado en Química for HRMS analyses and to Dr. Luis Espinoza for valuable help with spectroscopic assignments

Bioinspired Synthesis of Platensimycin from Natural ent-Kaurenoic Acids

Ministerio de Economía y Competitividad, PID2019-106222RB-C32/SRA (State Research Agency, 10.13039/501100011033)Universidad de Granada/CBU

Communic Acids: Occurrence, Properties and Use as Chirons for the Synthesis of Bioactive Compounds

Communic acids are diterpenes with labdane skeletons found in many plant species, mainly conifers, predominating in the genus Juniperus (fam. Cupresaceae). In this review we briefly describe their distribution and different biological activities (anti- bacterial, antitumoral, hypolipidemic, relaxing smooth muscle, etc.). This paper also includes a detailed explanation of their use as chiral building blocks for the synthesis of bioactive natural products. Among other uses, communic acids have proven useful as chirons for the synthesis of quassinoids (formal), abietane antioxidants, ambrox and other perfume fixatives, podolactone herbicides, etc., featuring shorter and more efficient processes

A Minor Dihydropyran Apocarotenoid from Mated Cultures of Blakeslea trispora

The heterocyclic C15 apocarotenoid 1 was isolated from mated cultures of the strains F986 (+) and F921 (−) of Blakeslea trispora. This new compound formed during sexual interaction is a minor constituent of the culture media and its structure was elucidated by spectroscopic data, including 2D-NMR. A plausible biosynthetic pathway involving a double degradation of β-carotene, followed by several oxidations of the resulting monocyclofarnesane C15 fragment is proposed.This research was financed by Junta de Andalucía (Grants FQM 340, CVI 910, and P08-CVI-03901) and the Spanish Government (Grant CTQ 2010-16818, subprogram BQ)

919-8 High-speed Coronary Rotational Atherectomy. Are Angiographic Factors Predictive of Failure, Major Complications or Restenosis? A Multivariate Analysis

In order to determine if angiographic factors are predictive of Failure (F), Major Complications (Me) or Restenosis (R) after Rotational Atherectomy with Rotablator, 16 angiographic variables were analyzed in 243 coronary arteries of 228 patients using a multivariate logistic regression technique (quasi Newton method and maximal probability technique).F was defined as the impossibility to complete the procedure; MC as the occurrence of O-wave myocardial infarctiön, in-hospital death or the need for emergency bypass graft surgery; R as recurrent ischemia due to an angiographic reduction of the lumen of the culprit vessel within 6 months following the procedure.Angiographic variables analized were: 1: Vessel treated. 2: Type of obstruction (A-B-C Task Force AHA-ACC). 3: Lesion lenhgth. 4: Lesion eccentricity. 5: Lesion angulation. 6: Lesion calcification. 7: Ostial lesion. 8: Lesion at a bifurcation. 9: Restenosed lesion. 10: Preprocedural stenosis. 11’ Postatherectomy stenosis. 12: Final stenosis. 13: Difficult access. 14: Number of vessels diseased>70% (1 vessel/multiple vessels). 15: Ejection fraction (40%/>40%).16: Arterial diameter (<3 mm/>3 mm).Primary success rate was 95.5% (232/243 arteries) and MC rate was 1.7% (infarction 2 cases and coronary surgery 2 cases, no deaths were recorded). F occurred in 6 cases.None of the covariates analized was statistically significant for F or MC. R was observed in 28.3% of cases and was 1.86 times more likely in longer lesions (p<0.03) and 2.54 times more likely in non calcified lesions (p<0.04). When lesion length and the presence of calcium were associated in a logistic regression manner, the following was obtained:LengthCalciumRestenosis % probability<10mm+6.3%10-20 mm+11.1%>20mm+18.9%<10 mm-14.6%10-20 mm-24.2%>20mm-37.2Conclusions1) The angiographic variables considered were not prediclive of F or Me. 2) Restenosis ocurred more frequenlly in long and non calcified lesions

Article Germacrone Derivatives as new Insecticidal and Acaricidal Compounds: A Structure-Activity Relationship

The supplementary material related to this article includes NMR spectra of new compounds is available online at https://www.mdpi.com/1420-3049/24/16/2898/s1.Currently, the use of synthetic pesticides is the main method of plant protection applied in agri- and horticulture. However, its excessive use leads to the development of pesticide resistance, a contamination of the environment, toxicity to non-target organisms, and risks for human health. With the ultimate aim of contributing to the develop of a more sustainable pest management, we used the natural product germacrone (compound 1), reported to possess significant insecticidal activity, as starting material for the generation of molecular diversity (2–24). Some of the generated derivatives are natural compounds, such as 1,10-epoxygermacrone (2), 4,5-epoxygermacrone (3), gajutsulactone A (7), germacrol (11), isogermacrone (14), 9-hydroxyeudesma-3,7(11)dien-6-one (19), eudesma-4,7(11),dien-8-one (20), eudesma-3,7(11)-dien-8-one (21) and eudesma-4(15),7(11)-dien-8-one (22). Compounds, 7,11-9,10-diepoxigermacr-4,5-en-8-ol (17), 7,11-epoxieudesma-4,7(11)-dien-8-one (23) and 7,11-epoxieudesma-3,7(11)-dien-8-one (24) are described for the first time. The biocidal activity of most of these compounds was assayed against the tick Hyalomma lusitanicum. The acaricidal effects of compound 24 were four times higher than that of germacrone (1). Compound 2 is an insect antifeedant a thousand times more potent than germacrone against Rhopalosiphum padi, which makes this substance a promising selective antifeedant against this cereal pest.This research was funded by Grant CTQ-2015-64049-C3-3-R/CTQ2015-64049-C3-1-R; MINISTERIO DE ECONOMÍA Y COMPETITIVIDAD, Spain (MINECO/FEDER)

The SlCBL10 calcineurin B-like protein ensures plant growth under salt stress by regulating Na+ and Ca2+ homeostasis

[EN] Characterization of a new tomato (Solanum lycopersicum) T-DNA mutant allowed for the isolation of the CALCINEURIN B-LIKE PROTEIN 10 (SlCBL10) gene whose lack of function was responsible for the severe alterations observed in the shoot apex and reproductive organs under salinity conditions. Physiological studies proved that SlCBL10 gene is required to maintain a proper low Na+/Ca2+ ratio in growing tissues allowing tomato growth under salt stress. Expression analysis of the main responsible genes for Na+ compartmentalization (i.e. Na+/H+ EXCHANGERs, SALT OVERLY SENSITIVE, HIGH-AFFINITY K+ TRANSPORTER 1; 2, H+-pyrophosphatase AVP1 [SlAVP1] and V-ATPase [SlVHA-A1]) supported a reduced capacity to accumulate Na+ in Slcbl10 mutant leaves, which resulted in a lower uploading of Na+ from xylem, allowing the toxic ion to reach apex and flowers. Likewise, the tomato CATION EXCHANGER 1 and TWO-PORE CHANNEL 1 (SlTPC1), key genes for Ca2+ fluxes to the vacuole, showed abnormal expression in Slcbl10 plants indicating an impaired Ca2+ release from vacuole. Additionally, complementation assay revealed that SlCBL10 is a true ortholog of the Arabidopsis (Arabidopsis thaliana) CBL10 gene, supporting that the essential function of CBL10 is conserved in Arabidopsis and tomato. Together, the findings obtained in this study provide new insights into the function of SlCBL10 in salt stress tolerance. Thus, it is proposed that SlCBL10 mediates salt tolerance by regulating Na+ and Ca2+ fluxes in the vacuole, cooperating with the vacuolar cation channel SlTPC1 and the two vacuolar H+-pumps, SlAVP1 and SlVHA-A1, which in turn are revealed as potential targets of SlCBL10.This study was supported by grants from the Plant KBBE Program (EUI2009-04074), the Spanish Ministerio de Economia y Competitividad (AGL2012-40150, AGL2015-64991-C3-1-R/2-R/3-R, and BIO2016-79187-R), as well as the French National Research Agency ENDOREPIGEN project. A.O.-A. was supported by a PhD fellowship from the Ministerio de Economia y Competitividad (BIO2009-11484).Egea, I.; Pineda Chaza, BJ.; Ortiz Atienza, A.; Plasencia, F.; Drevensek, S.; García Sogo, B.; Yuste-Lisbona, FJ.... (2018). The SlCBL10 calcineurin B-like protein ensures plant growth under salt stress by regulating Na+ and Ca2+ homeostasis. PLANT PHYSIOLOGY. 176(2):1676-1693. https://doi.org/10.1104/pp.17.01605S16761693176