Readily available Ti-beta as an efficient catalyst for greener and sustainable production of campholenic aldehyde

[EN] Different Ti-beta zeolite samples were prepared following a convenient and optimized post-synthetic route and starting from commercial Al-beta zeolite. Lewis acid sites have been successfully incorporated into vacant tetrahedral (T)-sites of a dealuminated beta-framework by ball-milling solid-state ion-exchange. A tribology-ball milling process was used in order to increase the interaction between dealuminated-beta zeolite and the Ti-precursor. Thermal treatments with water and aqueous solution of NaNO or Li NO allowed optimization of the catalytic properties of the Ti-Lewis active sites which exhibited excellent catalytic activity and stability for the isomerization of ¿-pinene oxide into campholenic aldehyde in both batch and fixed bed reactor systems. Additionally, the catalytic performance of the post-synthesised Ti-beta zeolite was compared to a Ti-beta zeolite prepared in fluoride media. From different points of view such as preparation of readily, highly active, selective and stable catalysts, throughput, sustainability and cost, herein we report the selective solid catalysed ¿-PO isomerization with excellent results, 88% selectivity and yield, a CA production of 225 g g h and new opportunities.The authors are grateful for financial support from the Spanish Government by MAT2017-82288-C2-1-P and Severo Ochoa Excellence Program SEV-2016-0683. The contribution of Mr. Pablo Ramos to the experimental work is also gratefully acknowledged.Puche Panadero, M.; Velty, A. (2019). Readily available Ti-beta as an efficient catalyst for greener and sustainable production of campholenic aldehyde. Catalysis Science & Technology. 9(16):4293-4303. https://doi.org/10.1039/c9cy00957dS42934303916Stekrova, M., Kumar, N., Aho, A., Sinev, I., Grünert, W., Dahl, J., … Murzin, D. Y. (2014). 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Unseeded synthesis of Al-free Ti-β zeolite in fluoride medium: a hydrophobic selective oxidation catalyst. Chem. Commun., (20), 2367-2368. doi:10.1039/cc9960002367Li, P., Liu, G., Wu, H., Liu, Y., Jiang, J., & Wu, P. (2011). Postsynthesis and Selective Oxidation Properties of Nanosized Sn-Beta Zeolite. The Journal of Physical Chemistry C, 115(9), 3663-3670. doi:10.1021/jp1076966Dijkmans, J., Gabriëls, D., Dusselier, M., de Clippel, F., Vanelderen, P., Houthoofd, K., … Sels, B. F. (2013). Productive sugar isomerization with highly active Sn in dealuminated β zeolites. Green Chemistry, 15(10), 2777. doi:10.1039/c3gc41239cHammond, C., Conrad, S., & Hermans, I. (2012). Simple and Scalable Preparation of Highly Active Lewis Acidic Sn-β. Angewandte Chemie International Edition, 51(47), 11736-11739. doi:10.1002/anie.201206193Wolf, P., Hammond, C., Conrad, S., & Hermans, I. (2014). 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Active Base Hybrid Organosilica Materials based on Pyrrolidine Builder Units for Fine Chemicals Production

[EN] The catalytic activity of "pyrrolidine type" fragments included or anchored in the mesoporous silica supports or polymeric frameworks have been fully reported for enantioselective transformation. Nevertheless, low attention was focused on their catalytic abilities to perform base-catalyzed reaction. Accordingly, hybrid materials including pyrrolidine fragments in the mesoporous silica supports were prepared following different synthesis methods, such as micellar and fluoride sol-gel routes in absence of structural directing agents. Their great catalytic performance was explored for various base-catalyzed reactions to the formation of C-C bond through Knoevenagel, Claisen-Schmidt and Henry condensations under microwave irradiation. The benefits of microwave irradiation combined with suitable catalytic properties of pyrrolidine hybrid materials with strong base sites and high accessibility to active centers, allowed carrying out successfully base-catalyzed condensation reactions for the production of fine chemicals. Moreover, the hybrid catalyst exhibited high selectivity and good stability over different catalytic cycles contributing to environmental sustainability.The authors are grateful for financial support from the Spanish Government, MAT2017-82288-C2-1-P and PID2020112590GB C21/AEI/10.13039/501100011033, and MULTY2HYCAT European project (EUHorizon 2020 funded project under grant agreement no. 720783).Llopis-Perez, S.; Velty, A.; Díaz Morales, UM. (2021). Active Base Hybrid Organosilica Materials based on Pyrrolidine Builder Units for Fine Chemicals Production. ChemCatChem. 13(23):5012-5024. https://doi.org/10.1002/cctc.202101031S50125024132

Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas

[EN] Three families of organosiliceous materials with different structuration level, order, and textural properties (non-ordered, M41S, and SBA-15 type materials) were prepared incorporating in their structural framework chiral pyrrolidine units with variable content. Likewise, non-ordered mesoporous hybrid solids were obtained through a sol-gel process in a fluoride medium, while M41S and SBA-15 type materials were obtained through micellar routes in the presence of long-chain neutral surfactants or block copolymers. Thanks to appropriate characterization studies and catalytic tests for the Michael addition between butyraldehyde and beta-nitrostyrene, we showed how the void shapes and sizes present in the structure of hybrid materials control the diffusion of reactants and products, as well as confine transition states and reactive intermediates. The best catalytic results, considering activity and enantioselectivity, were achieved in the presence of a non-ordered material, NOH-Pyr-5%, which exhibited the highest Brunauer-Emmett-Teller (BET) area, with a 96% yield and a 82% ee for the Michael adduct.This research was funded by the Spanish Government(MAT2017-82288-C2-1-P), Severo Ochoa Excellence Program (SEV-2016-0683), and MULTY2HYCAT (EU-Horizon 2020 funded project under grant agreement no. 720783). S. Ll. is thankful for the predoctoral fellowship from MINECO for financial support (BES-2015-072627).Llopis-Perez, S.; Velty, A.; Díaz Morales, UM. (2019). Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas. Catalysts. 9(8):1-21. https://doi.org/10.3390/catal9080654S12198Kuschel, A., Drescher, M., Kuschel, T., & Polarz, S. (2010). Bifunctional Mesoporous Organosilica Materials and Their Application in Catalysis: Cooperative Effects or Not? Chemistry of Materials, 22(4), 1472-1482. doi:10.1021/cm903412eDíaz, U., Brunel, D., & Corma, A. (2013). Catalysis using multifunctional organosiliceous hybrid materials. Chemical Society Reviews, 42(9), 4083. doi:10.1039/c2cs35385gKadib, A. E., Molvinger, K., Guimon, C., Quignard, F., & Brunel, D. (2008). Design of Stable Nanoporous Hybrid Chitosan/Titania as Cooperative Bifunctional Catalysts. Chemistry of Materials, 20(6), 2198-2204. doi:10.1021/cm800080sHorcajada, P., Serre, C., Vallet-Regí, M., Sebban, M., Taulelle, F., & Férey, G. (2006). Metal–Organic Frameworks as Efficient Materials for Drug Delivery. Angewandte Chemie International Edition, 45(36), 5974-5978. doi:10.1002/anie.200601878Zhang, J., Han, X., Wu, X., Liu, Y., & Cui, Y. (2019). Chiral DHIP- and Pyrrolidine-Based Covalent Organic Frameworks for Asymmetric Catalysis. ACS Sustainable Chemistry & Engineering, 7(5), 5065-5071. doi:10.1021/acssuschemeng.8b05887Loy, D. A., & Shea, K. J. (1995). Bridged Polysilsesquioxanes. Highly Porous Hybrid Organic-Inorganic Materials. Chemical Reviews, 95(5), 1431-1442. doi:10.1021/cr00037a013Inagaki, S., Guan, S., Fukushima, Y., Ohsuna, T., & Terasaki, O. (1999). Novel Mesoporous Materials with a Uniform Distribution of Organic Groups and Inorganic Oxide in Their Frameworks. Journal of the American Chemical Society, 121(41), 9611-9614. doi:10.1021/ja9916658Villaverde, G., Arnanz, A., Iglesias, M., Monge, A., Sánchez, F., & Snejko, N. (2011). Development of homogeneous and heterogenized rhodium(i) and palladium(ii) complexes with ligands based on a chiral proton sponge building block and their application as catalysts. Dalton Transactions, 40(37), 9589. doi:10.1039/c1dt10597cMelde, B. J., Holland, B. T., Blanford, C. F., & Stein, A. (1999). Mesoporous Sieves with Unified Hybrid Inorganic/Organic Frameworks. Chemistry of Materials, 11(11), 3302-3308. doi:10.1021/cm9903935García-García, P., Moreno, J. M., Díaz, U., Bruix, M., & Corma, A. (2016). Organic–inorganic supramolecular solid catalyst boosts organic reactions in water. Nature Communications, 7(1). doi:10.1038/ncomms10835Moreno, J. M., Velty, A., Díaz, U., & Corma, A. (2019). Synthesis of 2D and 3D MOFs with tuneable Lewis acidity from preformed 1D hybrid sub-domains. Chemical Science, 10(7), 2053-2066. doi:10.1039/c8sc04372hSzőllősi, G., Gombkötő, D., Mogyorós, A. Z., & Fülöp, F. (2018). Surface-Improved Asymmetric Michael Addition Catalyzed by Amino Acids Adsorbed on Laponite. Advanced Synthesis & Catalysis, 360(10), 1992-2004. doi:10.1002/adsc.201701627Feng, J., Li, X., & Cheng, J.-P. (2017). Enantioselective Organocatalyzed Vinylogous Michael Reactions of 3-Alkylidene Oxindoles with Enals. The Journal of Organic Chemistry, 82(3), 1412-1419. doi:10.1021/acs.joc.6b02582Bernardi, L., Fochi, M., Carbone, R., Martinelli, A., Fox, M. E., Cobley, C. J., … Carlone, A. (2015). Organocatalytic Asymmetric Conjugate Additions to Cyclopent-1-enecarbaldehyde: A Critical Assessment of Organocatalytic Approaches towards the Telaprevir Bicyclic Core. Chemistry - A European Journal, 21(52), 19208-19222. doi:10.1002/chem.201503352Afewerki, S., Ma, G., Ibrahem, I., Liu, L., Sun, J., & Córdova, A. (2015). Highly Enantioselective Control of Dynamic Cascade Transformations by Dual Catalysis: Asymmetric Synthesis of Polysubstituted Spirocyclic Oxindoles. ACS Catalysis, 5(2), 1266-1272. doi:10.1021/cs501975uMonge-Marcet, A., Pleixats, R., Cattoën, X., Man, M. W. C., Alonso, D. A., & Nájera, C. (2011). Prolinamide bridged silsesquioxane as an efficient, eco-compatible and recyclable chiral organocatalyst. New Journal of Chemistry, 35(12), 2766. doi:10.1039/c1nj20516aSagamanova, I., Rodríguez-Escrich, C., Molnár, I. G., Sayalero, S., Gilmour, R., & Pericàs, M. A. (2015). Translating the Enantioselective Michael Reaction to a Continuous Flow Paradigm with an Immobilized, Fluorinated Organocatalyst. ACS Catalysis, 5(11), 6241-6248. doi:10.1021/acscatal.5b01746Betancort, J. M., & Barbas, C. F. (2001). Catalytic Direct Asymmetric Michael Reactions:  Taming Naked Aldehyde Donors. Organic Letters, 3(23), 3737-3740. doi:10.1021/ol016700

Expandable Layered Hybrid Materials Based on Individual 1D Metalorganic Nanoribbons

[EN] Different metalorganic lamellar hybrid materials based on associated nanoribbons were synthesized by the use of alkyl-benzyl monocarboxylate spacers, containing alkyl tails with variable lengths, which acted like structural growing inhibitors. These molecular agents were perpendicularly located and coordinated to aluminium nodes in the interlayer space, controlling the separation between individual structure sub-units. The hybrid materials were studied by X-ray diffraction (XRD), chemical and thermogravimetrical analysis (TGA), nuclear magnetic resonance (NMR) and infrared spectroscopy (IR), and field emission scanning electron microscopy (FESEM)/transmission electron microscopy (TEM), showing their physicochemical properties. The specific capacity of the metalorganic materials to be exfoliated through post-synthesis treatments, using several solvents due to the presence of 1D structure sub-units and a marked hydrophobic nature, was also evidenced.The authors are grateful for financial support from the Spanish Government by MAT2017-82288-C2-1-P and Severo Ochoa Excellence Program SEV-2016-0683. J. M. M. acknowledges Predoctoral Fellowships from MINECO for economical support. The authors thank the MULTY2HYCAT EU-Horizon 2020 funded project under grant agreement no.720783.Moreno-Rodríguez, JM.; Velty, A.; Díaz Morales, UM. (2019). Expandable Layered Hybrid Materials Based on Individual 1D Metalorganic Nanoribbons. Materials. 12(12):1-13. https://doi.org/10.3390/ma12121953S1131212Nakagawa, K., Yamaguchi, K., Yamada, K., Sotowa, K.-I., Sugiyama, S., & Adachi, M. (2012). Synthesis and Characterization of Surface-Functionalized Layered Titanate Nanosheets Using Lamellar Self-Assembly as a Template. 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Zeolite-Assisted Lignin-First Fractionation of Lignocellulose: Overcoming Lignin Recondensation through Shape-Selective Catalysis

This is the peer reviewed version of the following article: E. Subbotina, A. Velty, J. S. M. Samec, A. Corma, ChemSusChem 2020, 13, 4528, which has been published in final form at https://doi.org/10.1002/cssc.202000330. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Organosolv pulping releases reactive monomers from both lignin and hemicellulose by the cleavage of weak C-O bonds. These monomers recombine to form undesired polymers through the formation of recalcitrant C-C bonds. Different strategies have been developed to prevent this process by stabilizing the reactive monomers (i.e., lignin-first approaches). To date, all reported approaches rely on the addition of capping agents or metal-catalyzed stabilization reactions, which usually require high pressures of hydrogen gas. Herein, a metal- and additive-free approach is reported that uses zeolites as acid catalysts to convert the reactive monomers into more stable derivatives under organosolv pulping conditions. Experiments with model lignin compounds showed that the recondensation of aldehydes and allylic alcohols produced by the cleavage of beta-O-4 ' bonds was efficiently inhibited by the use of protonic beta zeolite. By applying a zeolite with a preferred pore size, the bimolecular reactions of reactive monomers were effectively inhibited, resulting in stable and valuable monophenolics. The developed methodology was further extended to birch wood to yield monophenolic compounds and value-added products from carbohydrates.This work was supported by the Swedish Energy Agency, Stiftelsen Olle Engkvist Byggm~stare, and the European Union through ERC-AdG-2014-671093-SynCatMatch.Subbotina, E.; Velty, A.; Samec, JSM.; Corma Canós, A. (2020). 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Joule, 1(3), 613-622. doi:10.1016/j.joule.2017.10.004Kumaniaev, I., Subbotina, E., Sävmarker, J., Larhed, M., Galkin, M. V., & Samec, J. S. M. (2017). Lignin depolymerization to monophenolic compounds in a flow-through system. Green Chemistry, 19(24), 5767-5771. doi:10.1039/c7gc02731aVan den Bosch, S., Renders, T., Kennis, S., Koelewijn, S.-F., Van den Bossche, G., Vangeel, T., … Sels, B. F. (2017). Integrating lignin valorization and bio-ethanol production: on the role of Ni-Al2O3catalyst pellets during lignin-first fractionation. Green Chemistry, 19(14), 3313-3326. doi:10.1039/c7gc01324hDusselier, M., Van Wouwe, P., Dewaele, A., Jacobs, P. A., & Sels, B. F. (2015). Shape-selective zeolite catalysis for bioplastics production. Science, 349(6243), 78-80. doi:10.1126/science.aaa7169Zhang, L., Xi, G., Chen, Z., Jiang, D., Yu, H., & Wang, X. (2017). Highly selective conversion of glucose into furfural over modified zeolites. 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Designing bifunctional acid-base mesoporous hybrid catalysts for cascade reactions

[EN] Bifunctional mesoporous hybrid materials, containing both proton sponges and acid groups, have been prepared following different synthetic routes: co-condensation processes (sol-gel or micellar one-pot routes) or post-synthetic grafting of the organic functionalities. 1,8-Bis(dimethylamino)naphthalene (DMAN), a proton sponge with high pK(a), was used as an organic functional builder base and 3-mercaptopropyltriethoxysilane (MPTES) as a pendant precursor of sulfonic acids. The bifunctional hybrid materials were extensively characterized and were investigated as heterogeneous catalysts for various one-pot C-C bond-forming cascade reactions such as deacetalization-Knoevenagel condensation or deacetalization-nitroaldol (Henry) reaction.The authors thank the Spanish Government for financial support by Consolider-Ingenio MULTICAT CSD2009-00050, MAT2011-29020-C02-01 and Severo Ochoa Excellence Program SEV-2012-0267. EG thanks the Marie Curie Fellowship (FP7-PEOPLE-2009-IEF) for financial support.Gianotti, E.; Díaz Morales, UM.; Velty, A.; Corma Canós, A. (2013). Designing bifunctional acid-base mesoporous hybrid catalysts for cascade reactions. Catalysis Science and Technology. 3(10):2677-2688. https://doi.org/10.1039/c3cy00269aS26772688310Shylesh, S., & Thiel, W. R. (2010). Bifunctional Acid-Base Cooperativity in Heterogeneous Catalytic Reactions: Advances in Silica Supported Organic Functional Groups. ChemCatChem, 3(2), 278-287. doi:10.1002/cctc.201000353Sharma, K. K., Buckley, R. P., & Asefa, T. (2008). Optimizing Acid−Base Bifunctional Mesoporous Catalysts for the Henry Reaction: Effects of the Surface Density and Site Isolation of Functional Groups. Langmuir, 24(24), 14306-14320. doi:10.1021/la8030107Bass, J. D., Solovyov, A., Pascall, A. J., & Katz, A. (2006). 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Journal of the American Chemical Society, 126(4), 1010-1011. doi:10.1021/ja0398161Huh, S., Chen, H.-T., Wiench, J. W., Pruski, M., & Lin, V. S.-Y. (2005). Cooperative Catalysis by General Acid and Base Bifunctionalized Mesoporous Silica Nanospheres. Angewandte Chemie International Edition, 44(12), 1826-1830. doi:10.1002/anie.200462424Shiju, N. R., Alberts, A. H., Khalid, S., Brown, D. R., & Rothenberg, G. (2011). Mesoporous Silica with Site-Isolated Amine and Phosphotungstic Acid Groups: A Solid Catalyst with Tunable Antagonistic Functions for One-Pot Tandem Reactions. Angewandte Chemie International Edition, 50(41), 9615-9619. doi:10.1002/anie.201101449Motokura, K., Tomita, M., Tada, M., & Iwasawa, Y. (2008). Acid-Base Bifunctional Catalysis of Silica-Alumina-Supported Organic Amines for Carbon-Carbon Bond-Forming Reactions. Chemistry - A European Journal, 14(13), 4017-4027. doi:10.1002/chem.200702048Huang, Y., Xu, S., & Lin, V. S.-Y. (2010). 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Growing modulator agents for the synthesis of Al-MOF-type materials based on assembled 1D structural sub-domains

[EN] Novel aluminium MOF-type materials structured by 1D subdomains, such as organic-inorganic nanoribbons, were synthesized by modifying the conditions of solvothermal synthesis and the nature of the solvents in the presence of aryl monocarboxylate linkers with long alkyl chains, which acted as growth-modulating agents. Specifically, three different families of materials were prepared with various morphological characteristics: (i) isoreticular MIL-53(Al)-type materials, (ii) mesoscopic metalorganic structures and (iii) lamellar aluminium MOFs. The length of the alkyl chain in the aryl linker and the hydrophobic/hydrophilic nature of the solvothermal synthesis media determined the structuration level that was achieved. The derived Al-MOFs are active and stable catalysts for the synthesis of fine chemicals. This was illustrated by the efficient synthesis of 2,3-dihydro-2,2,4-trimethyl-1H-1,5-benzodiazepine.The authors are grateful for financial support from the Spanish Government under MAT2014-52085-C2-1-P, MAT2017-82288-C2-1-P and Severo Ochoa Excellence Program SEV-2016-0683. J. M. M. thanks predoctoral fellowships from MINECO for economic support. The European Union is also acknowledged for ERC-AdG-2014-671093-SynCatMatchMoreno, JM.; Velty, A.; Vidal Moya, JA.; Díaz Morales, UM.; Corma Canós, A. (2018). Growing modulator agents for the synthesis of Al-MOF-type materials based on assembled 1D structural sub-domains. Dalton Transactions. 47(15):5492-5502. https://doi.org/10.1039/C8DT00394GS549255024715Li, B., Wen, H.-M., Wang, H., Wu, H., Tyagi, M., Yildirim, T., … Chen, B. (2014). A Porous Metal–Organic Framework with Dynamic Pyrimidine Groups Exhibiting Record High Methane Storage Working Capacity. 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Advanced zeolite and ordered mesoporous silica-based catalysts for the conversion of CO2 to chemicals and fuels

For many years, capturing, storing or sequestering CO from concentrated emission sources or from air has been a powerful technique for reducing atmospheric CO. Moreover, the use of CO as a C1 building block to mitigate CO emissions and, at the same time, produce sustainable chemicals or fuels is a challenging and promising alternative to meet global demand for chemicals and energy. Hence, the chemical incorporation and conversion of CO into valuable chemicals has received much attention in the last decade, since CO is an abundant, inexpensive, nontoxic, nonflammable, and renewable one-carbon building block. Nevertheless, CO is the most oxidized form of carbon, thermodynamically the most stable form and kinetically inert. Consequently, the chemical conversion of CO requires highly reactive, rich-energy substrates, highly stable products to be formed or harder reaction conditions. The use of catalysts constitutes an important tool in the development of sustainable chemistry, since catalysts increase the rate of the reaction without modifying the overall standard Gibbs energy in the reaction. Therefore, special attention has been paid to catalysis, and in particular to heterogeneous catalysis because of its environmentally friendly and recyclable nature attributed to simple separation and recovery, as well as its applicability to continuous reactor operations. Focusing on heterogeneous catalysts, we decided to center on zeolite and ordered mesoporous materials due to their high thermal and chemical stability and versatility, which make them good candidates for the design and development of catalysts for CO conversion. In the present review, we analyze the state of the art in the last 25 years and the potential opportunities for using zeolite and OMS (ordered mesoporous silica) based materials to convert CO into valuable chemicals essential for our daily lives and fuels, and to pave the way towards reducing carbon footprint. In this review, we have compiled, to the best of our knowledge, the different reactions involving catalysts based on zeolites and OMS to convert CO into cyclic and dialkyl carbonates, acyclic carbamates, 2-oxazolidones, carboxylic acids, methanol, dimethylether, methane, higher alcohols (COH), C (gasoline, olefins and aromatics), syngas (RWGS, dry reforming of methane and alcohols), olefins (oxidative dehydrogenation of alkanes) and simple fuels by photoreduction. The use of advanced zeolite and OMS-based materials, and the development of new processes and technologies should provide a new impulse to boost the conversion of CO into chemicals and fuels

Procedimiento y catalizadores para la acetalización de ß-cetoésteres

Referencia OEPM: P9902439.-- Fecha de solicitud: 16/05/1996.-- Titulares: Universidad Politécnica de Valencia (UPV), Consejo Superior de Investigaciones Científicas (CSIC).En la presente invención se describe la acetalización de ß- cetoesteres por reacción directa con alquilglicoles utilizando como catalizadores ácidos, zeolitas y zeotipos con anillos de 10 o más miembros, tales como: Beta, OFF, MOR, Omega, SSZ-24, ZSM- 12, ZSM-5, SSZ-33, SSZ-42, ITQ-7, MCM-22, NU-86, NU-87, ITQ-2, CIT-5, UTD-1 y tamices moleculares mesoporosos, obteniéndose los correspondientes etilendioxi acetales con altos rendimientos y selectividades. Además, es también objetivo de esta invención encontrar un procedimiento para la obtención de ß-cetoesteres.Peer reviewe