91 research outputs found
Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to beta-gamma-unsaturated alfa-ketimino esters
"This is an Accepted Manuscript of an article published by Taylor & Francis in Journal of Coordination Chemistry on 2018, available online: https://doi.org/10.1080/00958972.2018.1437422."[EN] In this paper, we report the application of chiral complexes of La(III) with pyBOX ligands as Lewis acid catalysts in the conjugate addition of malonic esters to N-tosyl imines derived from Ă,gamma-unsaturated alfa-keto esters to give the corresponding chiral alfa,Ă-dehydroamino esters. pyBOX complexes with La(III), Yb(III), Sc(III), and In(III) triflates were assessed in this reaction but only La(III) showed good activity and enantioselectivity, while Yb(III) provided the expected product with low yield and stereoselectivity, and the Sc(III) and In(III) complexes were completely inactive. The complex of La(OTf)3 with the diphenyl-pyBOX ligand prepared in situ provided the best results and allowed obtaining chiral Âż,Ă-dehydroamino esters 3 with excellent yields, E:Z diastereomeric ratios (29:71-99:1) and high enantiomeric excesses (20-95%). The reaction could be applied to imines having a substituted aromatic ring or a heterocycle attached to the double bond, although the presence of electron-withdrawing groups on the aromatic ring was detrimental for stereoselectivity. The reaction products were obtained with the S configuration at the stereogenic center and the Z configuration at the enamine double bond as determined by NOESY experiments and X-ray analysis. Based on the experimental results a stereochemical model involving a nine-coordinate La(III) species has been proposed.This work was supported by the Ministerio de Economia y Competitividad (MINECO-Gobierno de Espana) [grant number CTQ2013-47494-P].Espinosa, M.; Blay, G.; Cardona, L.; FernĂĄndez, I.; Muñoz Roca, MDC.; Pedro, J. (2018). Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to beta-gamma-unsaturated alfa-ketimino esters. Journal of Coordination Chemistry. 71(6):864-873. https://doi.org/10.1080/00958972.2018.1437422S864873716Yukawa, T., Seelig, B., Xu, Y., Morimoto, H., Matsunaga, S., Berkessel, A., & Shibasaki, M. (2010). Catalytic Asymmetric Aza-MoritaâBaylisâHillman Reaction of Methyl Acrylate: Role of a Bifunctional La(O-iPr)3/Linked-BINOL Complex. Journal of the American Chemical Society, 132(34), 11988-11992. doi:10.1021/ja103294aKodama, H., Ito, J., Hori, K., Ohta, T., & Furukawa, I. (2000). Lanthanide-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrones to alkenes using 3,3âČ-bis(2-oxazolyl)-1,1âČ-bi-2-naphthol (BINOL-Box) ligands. Journal of Organometallic Chemistry, 603(1), 6-12. doi:10.1016/s0022-328x(00)00024-3De Bettencourt-Dias, A., Barber, P. S., & Bauer, S. (2012). A Water-Soluble Pybox Derivative and Its Highly Luminescent Lanthanide Ion Complexes. Journal of the American Chemical Society, 134(16), 6987-6994. doi:10.1021/ja209572mComelles, J., Pericas, Ă., Moreno-Mañas, M., Vallribera, A., Drudis-SolĂ©, G., Lledos, A., ⊠Roces-FernĂĄndez, L. (2007). Highly Enantioselective Electrophilic Amination and Michael Addition of Cyclic ÎČ-Ketoesters Induced by Lanthanides and (S,S)-ip-pybox: The Mechanismâ„. The Journal of Organic Chemistry, 72(6), 2077-2087. doi:10.1021/jo0622678Sanchez-Blanco, A. I., Gothelf, K. V., & JĂžrgensen, K. A. (1997). Lanthanide-catalyzed endo- and enantioselective 1,3-dipolar cycloaddition reactions of nitrones with alkenes. Tetrahedron Letters, 38(45), 7923-7926. doi:10.1016/s0040-4039(97)10048-xDesimoni, G., Faita, G., Guala, M., & Pratelli, C. (2003). Different Lanthanide Ions and the Pybox Substituents Induce the Reverse of the Sense of Induction in the Enantioselective DielsâAlder Reaction between Acryloyloxazolidinone and Cyclopentadiene. The Journal of Organic Chemistry, 68(20), 7862-7866. doi:10.1021/jo034215dDesimoni, G., Faita, G., Filippone, S., Mella, M., Zampori, M. G., & Zema, M. (2001). A new and highly efficient catalyst for the enantioselective MukaiyamaâMichael reaction between ( E )-3-crotonoyl-1,3-oxazolidin-2-one and 2-trimethylsilyloxyfuran. Tetrahedron, 57(51), 10203-10212. doi:10.1016/s0040-4020(01)01055-9Sammis, G. M., Danjo, H., & Jacobsen, E. N. (2004). Cooperative Dual Catalysis: Application to the Highly Enantioselective Conjugate Cyanation of Unsaturated Imides. Journal of the American Chemical Society, 126(32), 9928-9929. doi:10.1021/ja046653nJiang, J., Ma, Z., & Castle, S. L. (2015). Bulky α,ÎČ-dehydroamino acids: their occurrence in nature, synthesis, and applications. Tetrahedron, 71(34), 5431-5451. doi:10.1016/j.tet.2015.06.001Li, B., Cooper, L. E., & van der Donk, W. A. (2009). Chapter 21 In Vitro Studies of Lantibiotic Biosynthesis. Methods in Enzymology, 533-558. doi:10.1016/s0076-6879(09)04821-6M.A. Blaskovich. In Handbook on Syntheses of Amino Acids. General Route to Amino Acids, p. 225, ACS and Oxford University Press, New York (2010).Espinosa, M., GarcĂa-Ortiz, A., Blay, G., Cardona, L., Muñoz, M. C., & Pedro, J. R. (2016). E,Z-Stereodivergent synthesis of N-tosyl α,ÎČ-dehydroamino esters via a MukaiyamaâMichael addition. RSC Advances, 6(19), 15655-15659. doi:10.1039/c5ra27354dEspinosa, M., Blay, G., Cardona, L., & Pedro, J. R. (2013). Corrigendum: Asymmetric Conjugate Addition of Malonate Esters to α,ÎČ-UnsaturatedN-Sulfonyl Imines: An Expeditious Route to Chiral ÎŽ-Aminoesters and Piperidones. Chemistry - A European Journal, 19(52), 17632-17632. doi:10.1002/chem.201304285X-ray data for compound 3bl: crystallized from hexane-EtOAc; C25H29SN1O8; Mr = 503.55; triclinic; space group = P1; a = 6.2550(2), b = 10.2870(4), c = 11.1380(5) Ă
; α = 69.333(2), ÎČ = 78.688(2), Îł = 82.555(2)°; V = 656.11(5) Ă
3; Z = 1; Ïcalcd = 1.274 Mg mâ3; ÎŒ = 0.170 mmâ1; F(0 0 0) = 266. A colorless crystal of 0.04 Ă 0.08 Ă 0.08 mm3 was used; 5797 [R(int) = 0.0682] total reflections were collected on a Enraf Nonius Kappa CCD equipped with a graphite monochromator and Mo Kα (λ = 0.71073 Ă
) radiation. The structures were solved by using direct methods with SHELXS-2014 and refined by using full matrix least squares on F2 with SHELXL-2014 [16]. Non-hydrogen atoms were refined anisotropically and hydrogens were obtained or placed in calculated positions refined by using idealized geometries (riding model) and assigned fixed isotropic displacement parameters. Final values were R = 0.0469 and ÏR = 0.1054. CCDC-1581116 contains the supplementary crystallographic data for this compound. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.Parsons, S., Flack, H. D., & Wagner, T. (2013). Use of intensity quotients and differences in absolute structure refinement. Acta Crystallographica Section B Structural Science Crystal Engineering and Materials, 69(3), 249-259. doi:10.1107/s205251921301001
Resurgence of vaccine-preventable diseases in Venezuela as a regional public health threat in the Americas
Venezuelaâs tumbling economy and authoritarian rule have precipitated an unprecedented humanitarian crisis. Hyperinflation rates now exceed 45,000%, and Venezuelaâs health system is in free fall. The country is experiencing a massive exodus of biomedical scientists and qualified healthcare professionals. Reemergence of arthropod-borne and vaccine-preventable diseases has sparked serious epidemics that also affect neighboring countries. In this article, we discuss the ongoing epidemics of measles and diphtheria in Venezuela and their disproportionate impact on indigenous populations. We also discuss the potential for reemergence of poliomyelitis and conclude that action to halt the spread of vaccine-preventable diseases within Venezuela is a matter of urgency for the country and the region. We further provide specific recommendations for addressing this crisis. © 2019 Centers for Disease Control and Prevention (CDC). All rights reserved
InfluĂȘncia da mistura de sulfato de amĂŽnio com urĂ©ia sobre a volatilização de nitrogĂȘnio amoniacal
Reproductive cycle of Mytella guyanensis (Lamarck, 1819) in a Marine Reserve (RESEX Bay of Iguape), Bahia, Brazil
Comparação de sistemas de avaliação de dietas para bovinos no modelo de produção intensiva de carne. Suplementação do pasto para vacas na estação seca
Desempenho de progĂȘnies de diferentes matrizes de cajuzinho-do-cerrado mediante o armazenamento e o peso das nĂșculas
Global monitoring of antimicrobial resistance based on metagenomics analyses of urban sewage
Antimicrobial resistance (AMR) is a serious threat to global public health, but obtaining representative data on AMR for healthy human populations is difficult. Here, we use meta-genomic analysis of untreated sewage to characterize the bacterial resistome from 79 sites in 60 countries. We find systematic differences in abundance and diversity of AMR genes between Europe/North-America/Oceania and Africa/Asia/South-America. Antimicrobial use data and bacterial taxonomy only explains a minor part of the AMR variation that we observe. We find no evidence for cross-selection between antimicrobial classes, or for effect of air travel between sites. However, AMR gene abundance strongly correlates with socio-economic, health and environmental factors, which we use to predict AMR gene abundances in all countries in the world. Our findings suggest that global AMR gene diversity and abundance vary by region, and that improving sanitation and health could potentially limit the global burden of AMR. We propose metagenomic analysis of sewage as an ethically acceptable and economically feasible approach for continuous global surveillance and prediction of AMR.Peer reviewe
Germinação de sementes de dalbergia nigra (Vell.) Allemao ex Benth. (Fabaceae-Papilionoideae) no armazenamento
Desafios polĂticos para a consolidação do Sistema Ănico de SaĂșde: uma abordagem histĂłrica
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