Síntesis de productos naturales y análogos biológicamente activos, derivados de Penicillium brevicompactum Dierckx

En la presente tesis se han desarrollado unas secuencias sintéticas que han permitido la confirmación de las estructuras de los metabolitos aislados previamente de Penicillium brevicompactum, bien sea por síntesis total de los mismos o por preparación de sustancias análogas que hacen inequívoca la asignación realizada en un principio. Por otro lado, se han utilizado las rutas sintéticas abiertas para la consecución de diferentes análogos con el fin de establecer relaciones estructura-actividad que permitan la optimización de las actividades observadas para los productos naturales aislados. Todo ello ha concluido con la confirmación de las importantes actividades presentadas por los productos naturales aislados, así como la optimización de las actividades fungicidas e insecticidas por obtención de análogos sintéticos.Cantin Sanz, A. (1998). Síntesis de productos naturales y análogos biológicamente activos, derivados de Penicillium brevicompactum Dierckx [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/5022Palanci

Diels-Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels-Alder reaction

Diels-Alder cycloaddition between cyclopentadiene and p-benzoquinone has been studied in the confined space of a pure silica zeolite Beta and the impact on reaction rate due to the concentration effect within the pore and diffusion limitations are discussed. Introduction of Lewis or Bronsted acid sites on the walls of the zeolite strongly increases the reaction rate. However, contrary to what occurs with mesoporous molecular sieves (MCM-41), Beta zeolite does not catalyse the retro-Diels-Alder reaction, resulting in a highly selective catalyst for the cycloaddition reaction.Financial support from the Ministerio de Economia y Competitividad through projects MAT2015-71261-R and CTQ2014-54987-P, are greatly acknowledged. M. V. Gomez thanks MINECO for participation in the Ramon y Cajal program. The authors thank M. Moliner, M. T. Navarro, S. Valencia for providing all the catalytic materials used in this study.Cantin Sanz, A.; Gomez, MV.; De La Hoz, A. (2016). Diels-Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels-Alder reaction. Beilstein Journal of Organic Chemistry. 12:2181-2188. https://doi.org/10.3762/bjoc.12.208S218121881

Use of different microporous and mesoporous materials as catalyst in the Diels-Alder and retro-Diels-Alder reaction between cyclopentadiene and p-benzoquinone

[EN] Diels-Alder cycloaddition between cyclopentadiene and p-benzoquinone has been studied using amorphous silica and different ITQ-2 and MCM-41 pure silica and metal containing materials as catalysts. The reaction can afford different products depending on the molecular reacting site. and the possibility of consecutive additions. Structured solid catalysts increase the selectivity to the endo-endo isomer. Silanol groups have not enough Bronsted acidity to interact with the carbonyl groups present in the dienophile. to reduce LUMO's energy and provide a better overlap between HOMO and LUMO. according to the frontier molecular orbital theory. The introduction of transition metal atoms in the framework increases the reaction rate for the Diels-Alder reaction while preserving the selectivity to the endo-endo isomer. The presence of more acidic OH groups enhance the retro-Diels-Alder reaction increasing (fie selectivity to the endo-exo isomer. (c) 2005 Elsevier B.V. All lights reserved.The authors thank CICYT (MAT 2003-07945-C02-01) for financial support. M.V. Gomez thanks Ministerio de Educacion y Ciencia ´ for the predoctoral grant.Gomez, MV.; Cantin Sanz, A.; Corma Canós, A.; Hoz, ADL. (2005). Use of different microporous and mesoporous materials as catalyst in the Diels-Alder and retro-Diels-Alder reaction between cyclopentadiene and p-benzoquinone. Journal of Molecular Catalysis A Chemical. 240(1):16-21. https://doi.org/10.1016/j.molcata.2005.06.030S1621240

Gold(I) catalyses the intermolecular hydroenamination of alkynes with imines and produces alfa,alfa',N-triarylbisenamines: studies on their use as intermediates in synthesis

[EN] alpha,alpha',N-Tnarylbisenamines have been efficiently formed and isolated for the first time The synthesis is based on an unprecedented gold(I)-catalyzed double intermolecular hydroamination between N-arylamines and aryl alkynes This reaction constitutes a new example of the intriguing behavior of gold as catalyst in organic synthesis The reactivity of these bisenamines for three different reactions, leading to potentially useful intermediates, is also shown In particular, hindered azabicycles [3 2 0], which present excellent UVA and UVB absorption properties, are obtained by addition of triarylbisenamines to propiolates following an unexpected mechanismThis work is dedicated to Prof Steven V Ley on the occasion of his 65th birthday A L-P thanks CSIC for a contract under the JAE-doctors program Financial support by the PLE2009 project form MCIINN and PRO-METEO from Generalitat Valenciana are also acknowledged We thank Dr I Andreu for discussions on UV results The Continuous support from the ITQ's NMR team is also particularly appreciatedLeyva Perez, A.; Cabrero Antonino, JR.; Cantin Sanz, A.; Corma Canós, A. (2010). Gold(I) catalyses the intermolecular hydroenamination of alkynes with imines and produces alfa,alfa',N-triarylbisenamines: studies on their use as intermediates in synthesis. The Journal of Organic Chemistry. 75(22):7769-7780. doi:10.1021/jo101674tS77697780752

Synthesis and biological evaluation of new analogues of the active fungal metabolites N-(2-methyl-3-oxodecanoyl)-2-pyrroline and N-(2-methyl-3-oxodec-enoyl)-2-pyrroline

[EN] To evaluate the effect of simplifying the ß-ketoamide system present in active isolated metabolites from Penicillium brevicompactum (2 and 3) on the activity, new analogues with a monocarbonylic amide functionality have been obtained. In this way, the insecticidal and fungicidal activities have been improved in relation to the natural products taken as lead molecules. Thus, two of the synthetic analogues (5a and 5b) showed very important insecticidal activities against third-instar nymphs of Oncopeltus fasciatus Dallas, with acute LD50 values of 3.0 and 1.5 ¿g/cm2, respectively. Moreover, some analogues showed good levels of fungicidal activity against a wide range of commercially important and taxonomically diverse fungi; remarkably, compound 7c has proved to be highly active against Colletotrichum gloesporoides and Colletotrichum coccodes, with ED50 values of 2.04 and 11.7 ¿g/mL, respectively.Moya Sanz, MDP.; Cantin Sanz, A.; Miranda Alonso, MÁ.; Primo Millo, J.; Primo Yufera, E. (1999). Synthesis and biological evaluation of new analogues of the active fungal metabolites N-(2-methyl-3-oxodecanoyl)-2-pyrroline and N-(2-methyl-3-oxodec-enoyl)-2-pyrroline. JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY. 47(9):3866-3871. doi:10.1021/jf990115q3866387147

Isolation of N-(2-Methyl-3-oxodecanoyl)pyrrole and N-(2-Methyl-3-oxodec-8-enoyl)pyrrole, Two New Natural Products from Penicillium brevicompactum, and Synthesis of Analogues with Insecticiidal and Fungicidal Activity

[EN] Two new natural products have been isolated from culture broth of Penicillium brevicompactum Dierckx. The structures have be en assigned as N-(2-methyl-3-oxodecanoyl)pyrrole and N-(2-methyl-3-oxodec-8-enoyl)pyrrole on the basis of spectral data. Synthesis of analogues has been carried out by acylation of the pyrrole ring at Ct with different acylated Meldrum's acids. Two analogues (6b and 7b) have shown interesting insecticidal activities, and three other ones (6a, 6c, and 7a) have exhibited significant broad-spectrum fungicidal activities. These synthetic products might be considered as a starting point in the search for new pesticides.Cantin Sanz, A.; Moya, P.; Miranda Alonso, MÁ.; Primo Millo, J.; Primo Yufera, E. (1998). Isolation of N-(2-Methyl-3-oxodecanoyl)pyrrole and N-(2-Methyl-3-oxodec-8-enoyl)pyrrole, Two New Natural Products from Penicillium brevicompactum, and Synthesis of Analogues with Insecticiidal and Fungicidal Activity. Journal of Agricultural and Food Chemistry. 46(11):4748-4753. doi:10.1021/jf9800763S47484753461

Elucidation of the Interaction Mechanism between Organic Chiral Cages with Biomolecules through Nuclear Magnetic Resonance and Theoretical Studies

[EN] A multinuclear NMR has been carried out to elucidate the mechanism of action of CC3-R box-type chiral materials for the separation of enantiomers, supported by theoretical calculations. The potential of these materials to be used as chiral resolution agents through NMR is evidence in this study.Program Severo Ochoa SEV-2016-0683 is gratefully acknowledged. S.S-F. thanks MEC for his Severo Ochoa Grant SPV-2013-067884, P.O.-B. thanks MEC for his Ramon y Cajal contract RYC-2014-16620. M.B. and F.R. thank the financial support by the Spanish Government (MAT2017-82288-C2-1-P and MAT2015-71842-P). The authors thank the MULTY2-HYCAT (EU-Horizon 2020 funded project under grant agreement no. 720783). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.Saez-Ferre, S.; Boronat Zaragoza, M.; Cantin Sanz, A.; Rey Garcia, F.; Oña-Burgos, P. (2018). Elucidation of the Interaction Mechanism between Organic Chiral Cages with Biomolecules through Nuclear Magnetic Resonance and Theoretical Studies. The Journal of Physical Chemistry C. 122(29):16821-16829. https://doi.org/10.1021/acs.jpcc.8b05069S16821168291222

Synthesis and Structure of the Bidimensional Zeolite ITQ-32 with Small and Large Pores

The authors thank to the Spanish CICYT for financial support (MAT2003-07945-C02-01, MAT2003-07769-C02-01, MAT2002-02808).Cantin Sanz, A.; Corma Canós, A.; Leiva, S.; Rey Garcia, F.; Rius, J.; Valencia Valencia, S. (2005). Synthesis and Structure of the Bidimensional Zeolite ITQ-32 with Small and Large Pores. Journal of the American Chemical Society. 127(33):11560-11561. https://doi.org/10.1021/ja053040hS11560115611273

Rational Design and HT Techniques Allow the Synthesis of New IWR Zeolite Polymorphs

The authors thank the Spanish CICYT for financial support (MAT2003-07945-C02-01). J.L.J. thanks the Spanish MEC for the Juan de la Cierva contract.Cantin Sanz, A.; Corma Canós, A.; Díaz Cabañas, MJ.; Jorda Moret, JL.; Moliner Marin, M. (2006). Rational Design and HT Techniques Allow the Synthesis of New IWR Zeolite Polymorphs. Journal of the American Chemical Society. 128(13):4216-4217. https://doi.org/10.1021/ja0603599S421642171281

Pure silica ITQ-32 zeolite allows separation of linear olefins from paraffins

[EN] ITQ-32 is able to separate propene from propane and represents a clear improvement with respect to previous zeolites in achieving the separation of trans-2-butene and 1-butene from the C(4) fraction using only one zeolite.Palomino Roca, M.; Cantin Sanz, A.; Corma Canós, A.; Leiva Herrero, S.; Rey Garcia, F.; Valencia Valencia, S. (2007). Pure silica ITQ-32 zeolite allows separation of linear olefins from paraffins. Chemical Communications. 12:1233-1235. doi:10.1039/b700358gS123312351