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Breast cancer is the leading cause of cancer death among women worldwide. For this reason, the development of new therapies is still essential. In this work we have analyzed the antitumor potential of levoglucosenone, a chiral building block derived from the pyrolysis of cellulose-containing materials such as soybean hulls, and three structurally related analogues. Employing human and murine mammary cancer models, we have evaluated the effect of our compounds on cell viability through MTS assay, apoptosis induction by acridine orange/ethidium bromide staining and/or flow cytometry and the loss of mitochondrial potential by tetramethylrhodamine methyl ester staining. Autophagy and senescence induction were also evaluated by Western blot and β-galactosidase activity respectively. Secreted metalloproteases activity was determined by quantitative zymography. Migratory capacity was assessed by wound healing assays while invasive potential was analyzed using Matrigel-coated transwell chambers. In vivo studies were also performed to evaluate subcutaneous tumor growth and experimental lung colonization. All compounds impaired in vitro proliferation with IC50 values in a range of low micromolar. Apoptosis was identified as the main mechanism responsible for the reduction of monolayer cell content induced by the compounds without detecting modulations of autophagy or senescence processes. Two of the four compounds (levoglucosenone and its brominated variant) were able to modulate in vitro events associated with tumor progression, such as migratory potential, invasiveness, and proteases secretion. Furthermore, tumor volume and metastatic spread were significantly reduced in vivo after the treatment these two compounds. Here, we could obtain from soybean hulls, a material with almost no commercial value, a variety of chemical compounds useful for breast cancer treatment.

The synthesis of selective inhibitors of human carbonic anhydrases (hCAs) is of paramount importance to avoid side effects derived from undesired interactions with isoforms not involved in the targeted pathology, and this was partially addressed with the introduction of a sugar moiety (the so-called "sugar approach"). Since glycomimetics are considered more selective than the parent sugars in inhibiting carbohydrate-processing enzyme, we explored the possibility of further tuning the selectivity of hCAs inhibitors by combining the sulfonamide moiety with a sugar analogue residue. In particular, we report the synthesis of two novel hCAs inhibitors 2 and 3 which feature the presence of a piperidine iminosugar and an additional carbohydrate moiety derived from levoglucosenone (1), a key intermediate derived from cellulose pyrolysis. Biological assays revealed that iminosugar 2 is a very strong inhibitor of the central nervous system (CNS) abundantly expressed hCA VII (KI of 7.4 nM) and showed a remarkable selectivity profile toward this isoform. Interestingly, the presence of levoglucosenone in glycomimetic 3 imparted a strong inhibitory activity toward the tumor associated hCA IX (KI of 35.9 nM). Fil: Pratesi, Debora. Università degli Studi di Firenze; Italia Fil: Matassini, Camilla. Università degli Studi di Firenze; Italia Fil: Goti, Andrea. Università degli Studi di Firenze; Italia Fil: Angeli, Andrea. Università degli Studi di Firenze; Italia Fil: Carta, Fabrizio. Università degli Studi di Firenze; Italia Fil: Supuran, Claudiu T.. Università degli Studi di Firenze; Italia Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Cardona, Francesca. Università degli Studi di Firenze; Italia

Fe de erratas del artículo Antineoplastic activity of products derived from cellulose-containing materials: levoglucosenone and structurally-related derivatives as new alternatives for breast cancer treatment. Fil: Delbart, Damian Ignacio. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Giri, Germán Francisco. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Cammarata, Agostina. Comisión Nacional de Energía Atómica. Gerencia de Investigación y Aplicaciones; Argentina. Fil: Pan, Melisa Denise. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Unidad de Transferencia Genética; Argentina. Fil: Bareño, Lizeth Ariza. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Amigo, Natalia Loreley. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Bechis, Andrés. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Suarez, Alejandra Graciela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Spanevello, Rolando Ángel. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Spanevello, Rolando Ángel. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina. Fil: Villaverde, Marcela Solange. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Unidad de Transferencia Genética; Argentina. Fil:Villaverde, Marcela Solange. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina. Fil: Todaro, Laura Beatriz. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Todaro, Laura Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina. Fil: Urtreger, Alejandro Jorge. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Urtreger, Alejandro Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina.

Purpose: Breast cancer is the leading cause of cancer death among women worldwide. For this reason, the development of new therapies is still essential. In this work we have analyzed the antitumor potential of levoglucosenone, a chiral building block derived from glucose, and three structurally related analogues obtained from soybean hulls pyrolysis.Methods: Employing human and murine mammary cancer models, we have evaluated the effect of our compounds on cell viability through MTS assay, apoptosis induction by acridine orange / ethidium bromide staining and/or flow cytometry and the loss of mitochondrial potential by tetramethylrhodamine methyl ester staining. Autophagy and senescence induction were also evaluated by Western blot and β-galactosidase activity respectively. Secreted metalloproteases activity was determined by quantitative zymography. Migratory capacity was assessed by wound healing assays while invasive potential was analyzed using Matrigel-coated transwell chambers. In vivo studies were also performed to evaluate subcutaneous tumor growth and experimental lung colonization.Results: Apoptosis was identified as the main mechanism responsible for the reduction of monolayer cell content induced by the compounds without detecting modulations of autophagy or senescence processes. Two of the four compounds were able to modulate in vitro events associated with tumor progression, such as migratory potential, invasiveness, and proteases secretion. Furthermore, tumor volume and metastatic spread were significantly reduced in vivo after treatment with the compounds.Conclusion: We could obtain from soybean hulls, a material with almost no commercial value, a variety of chemical compounds useful for breast cancer treatment.

Various international perspectives from selected regions where substantial work is being done on green and sustainable chemistry education emphasize a systems thinking framework. Common to most of the perspectives is the inclusion of more global paradigms involving economic, environmental, political, and social aspects as fundamental issues in the formerly merely technical and scientific discussions, as well as the development of laboratory experiences, training sessions, written materials, discussion meetings, and conferences. We include bird’s eye views from Europe (the Green Chemistry Centre of Excellence at the University of York, United Kingdom; the University of Cordoba, Spain; and the University of Amsterdam, The Netherlands), Latin America (the Universidad Nacional de Rosario, Argentina, and the Universidad Iberoamericana, Mexico), Africa (the University of Venda, South Africa), and Australia (Monash University).

The discovery of efficient organocatalysts is generally carried out by thorough experimental screening of different candidates. We recently reported an efficient organocatalyst for iminium-ion-based asymmetric Diels-Alder reactions following a rational design approach. This result encouraged us to test this optimal catalyst in the mechanistically related Friedel-Crafts alkylation of indoles, but to our surprise, almost null enantioselectivity was observed. The results did not significantly improve with structurally related catalysts, and a totally unexpected facial selectivity inversion was also noticed. Using DFT calculations by modeling the competing transition structures with ONIOM, we could unravel the origins of those findings, further employed to predict the most efficient catalyst for this new transformation. The computational results were validated experimentally (up to 92:8 er), providing another successful example of a general strategy to accelerate catalyst development which still remains underexplored. Fil: Gerosa, Gabriela Guillermina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Marcarino, Maribel Oriana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Fil: Comba, Maria Betina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Rosario. Instituto de Quimica Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquimicas y Farmaceuticas. Instituto de Quimica Rosario; Argentina

The need to find sustainable alternatives to reduce the dependence on fossil sources has led to significant research efforts on the conversion of biomass into platform chemicals. Modern organic chemistry requires easily obtainable chiral building blocks that show high chemical versatility for their application in the synthesis of enantiopure compounds. The selective pyrolytic conversion of cellulose or cellulose-containing materials produces levoglucosenone, a highly functionalized chiral structure. This compound has been innovatively used as a template for the synthesis of key intermediates of biologically active products and for the preparation of chiral auxiliaries, catalysts, and organocatalysts for their application in asymmetric synthesis.

[EN] Levoglucosenone, directly produced from cellulose-containing residual biomass via pyrolysis treatments, is believed to be a promising bio-renewable platform for both fine and commodity chemicals. In this work, the possibilities given by tuneable catalysts based on Pd and Pt supported on metallic oxides to produce the desired product in the one-pot hydrogenation of levoglucosenone are evaluated. Particularly, the excellent catalytic performance of Pd/ZrO2 and Pt/ZrO2 type materials for the synthesis of dihydrolevoglucosenone (or Cyrene) and levoglucosanol, respectively, during the mild hydrogenation of levoglucosenone is demonstrated. In the Cyrene synthesis, the Pd/t-ZrO2 material showed the best catalytic activity compared to other Pd-supported on metallic oxides. This catalyst achieved nearly 95% yields of Cyrene by working under mild reaction conditions, with very low catalyst loadings (¿3 wt%) and using water as the solvent. On the other hand, the one-pot hydrogenation of levoglucosenone to levoglucosanol is reported for the first time with a Pt-based heterogeneous catalyst (Pt/ZrO2-mix, yield ¿90%), by working at low temperatures and mild H2 pressures with water as the solvent. Comparison of the results attained with other Pt-supported metallic oxides let us to conclude that the metal crystal facets (specifically the 100 facet) play an important role in the hydrogenation process to give levoglucosanol selectively. In addition, the stability and re-usability of both catalysts under operational conditions are also evaluated. Finally, catalytic tests including the use of crude bio-liquids obtained from cellulose-rich biomass pyrolysis and containing ¿66 wt% of levoglucosenone are also assayed, thus demonstrating the possibility of scaling-up the process over these metals supported on zirconia catalysts., Financial support by the Spanish Government (CTQ-201567592, SEV-2016-0683 and PGC2018-097277-B-100) is gratefully acknowledged. R.S. thanks the CONICET financial support (CONICET-CSIC, PVCE Program, RD 4183/15). J.M. thanks MICINN (CTQ2015-67592) for the PhD fellowship. Authors also thank the Electron Microscopy Service of Universitat Politecnica de Valencia for their support.

The design and synthesis of X-shaped molecules bases on a central pyrene is reported. A Sonogashira cross-coupling reaction was applied to successfully bond the pyrene core through acetylene linkages to electroactive dendrons moieties such as triphenylamine or carbazole. Dendrons were functionalized with bulky alkyl groups to disrupt π-π stacking interactions and consequently affording soluble dendrimers. These novel π-conjugated turtle-shape dendrimers are organic materials with great potential applications in optoelectronic devices. Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Cappellari, María Victoria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Fungo, Fernando Gabriel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Diels–Alder cycloaddition between an enantiomerically pure protected cis-cyclohexadiene diol metabolite and optically pure levoglucosenone derived from cellulose gave rise to complex pentacyclic natural product like structures in a chemically succinct process. The adducts were fully characterized and the observed results were in accord with theoretical calculations performed on the possible course of the reaction.

A series of levoglucosenone-derived 1,2,3-triazoles and isoxazoles featuring a flexible spacer between the heteroaromatic and anhydropyranose cores have been designed and synthesized following an hetero Michael // 1,3-dipolar cycloaddition path. The use of a design of experiments approach allowed the optimization of the oxa-Michael reaction with propargyl alcohol as nucleophile, a key step for the synthesis of the target compounds. All of the compounds were tested for their anticancer activity on MDA-MB-231 cells, featuring mutant p53. The results highlighted the importance of the introduction of the flexible spacer as well as the higher activity of oxa-Michael isoxazole-derivatives. The most prominent compounds also showed anti-proliferative activities against lung and colon cancer cell lines. The compounds showed enhanced cytotoxic effects in the presence of mutant p53, determined both by endogenous mutant p53 knock down (R280K) and by reintroducing p53 R280K in cells lacking p53 expression.

The design and synthesis of novel dendrimeric structures derived from a pyrene core with substituted triphenylamine and carbazole periphery demonstrated how molecular engineering allowed the fine tuning of the electrogenerated chemiluminiscence (ECL) properties. These two compound (Py-CBZ and Py-TPA) in comparison with the parent structures (Py and Py-Core) showed better chemical stability and anti-aggregation capability. At the same time, the photophysical (Absλmax, E00FLλmaxΦFL), photochemical (oxygen quenching), electrochemical (redox potentials) and optoelectronic (HOMO-LUMO gap and their energy position) properties were modulated, resulting in obtaining two highly ECL emitting molecular structures (Py-CBZ and Py-TPA). This study showed that functionalization of organic dyes with redox moieties (with the proper linker and position) improved the radical stability and also, modulated the optoelectronic properties with the concomitant enhancement of the ECL performance and their potential use in applications such as organic light-emitting devices. Fil: Cappellari, María Victoria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Marzari, Gabriela Lorena. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Morales, Gustavo Marcelo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Fungo, Fernando Gabriel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

The design and synthesis of biomass-derived triazoles and the in vitro evaluation as potential anticancer agents are described. The discovery of base-catalyzed retro-aza-Michael//aza-Michael isomerizations allowed the exploration of the chemical space by affording novel types of triazoles, difficult to obtain otherwise. Following this strategy, 2,4-disubstituted 1,2,3-triazoles could be efficiently obtained from the corresponding 1,4-disubstituted analogues. Fil: Tsai, Yi Hsuan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Borini Etichetti, Carla Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Di Benedetto, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Girardini Brovelli, Javier Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Martins, Felipe Terra. Universidade Federal de Goiás; Brasil Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A family of structurally related π-conjugated star-shape bis-carbazol-triphenylamine end-caped dendrimers was designed, synthetized and characterized as novel organic optoelectronic materials. These compounds hold triphenylamine and carbazole electroactive moieties as dendrimer core and/or periphery groups. Homogeneous and stable electrogenerated polymeric films were obtained from dendrimers over Pt and ITO electrodes. These films showed charge conductivities, reversible electrochemical behavior and electrochromic effect. The hole mobility of the electrodeposited films was found to be dependent of the dendrimeric structure and film morphologies, indicating that the shape and size of the studied dendrimers have a strong effect on their charge transport properties. These results provide data that will contribute to the systematic study for the design of new dendrimers as starting materials for conductive polymers films with potential applications in optoelectronic devices. Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Minudri, Daniela. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquímicas y Naturales. Departamento de Química. Area Electroquímica; Argentina Fil: Cavallo, Pablo César. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquímicas y Naturales. Departamento de Química. Area Electroquímica; Argentina Fil: Otero, Luis Alberto. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquímicas y Naturales. Departamento de Química. Area Electroquímica; Argentina Fil: Fungo, Fernando Gabriel. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquímicas y Naturales. Departamento de Química. Area Electroquímica; Argentina

The trend for material and energy recovery from residues along with the need to reduce greenhouse gases has led to an increased interest in the thermal exploitation of biomass and/or their wastes. Due to the enormous quantity generated every year, agro-industrial byproducts have an attractive potential to be recycled. One way to do this is by means of pyrolysis, a thermal decomposition of high molecular weight polymers into simpler compounds. In this study, we applied an autographic assay to analyze the biological effect of bio-oils produced by pyrolysis of soybean hulls. The discovery of a compound with antimicrobial activity validated this novel approach as a tool for the generation of bioactive compounds. Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Viarengo, Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Furlan, Ricardo Luis Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Investigaciones para el Descubrimiento de Fármacos de Rosario. Universidad Nacional de Rosario. Instituto de Investigaciones para el Descubrimiento de Fármacos de Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Garcia Vescovi, Eleonora. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

The first application of chiral auxiliaries synthesized from levoglucosenone (a biomass-derived anhydrosugar) in asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides is herein reported. The corresponding pyrrolidinic cores were obtained in excellent levels of regio and stereocontrol, good to excellent π-facial selectivities, and could be isolated enantiomerically pure by column chromatography. Unexpected NMR observations coupled with DFT calculations allowed the stereochemical assignment of the synthesized adducts. The stereochemical assignment performed in silico was further unambiguously validated by structural X-ray diffraction analysis. Fil: Llompart, David Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Corne, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Castellano, Eduardo E.. Universidade de Sao Paulo; Brasil. Instituto de Física de São Carlos; Brasil

Fil: Testero, Sebastian Andres. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Rosario. Instituto de Quimica Rosario; Argentina

Alternative sources of starting materials Biomass is the source of renewable carbon that will allow to achieve the future development of our society. With the prospect of the fossil resources depletion, it is necessary to find new alternative sources of energy and raw materials. Chemistry will play a key role to design new materials from biomass which will reshape our way of living and consumption.

The 1,3-dipolar cycloaddition reactions of azomethine ylides is one of the preferred methods for the synthesis of polysubstituted pyrrolidines. The use of chiral dipolarophiles derived from carbohydrates yields enantiomerically pure pyrrolidines, usually in good to excellent endo selectivities, along with other minor stereoisomers. Recently, we found an unusual isomerization event that allowed the isolation of useful pyrrolidines with relative stereochemistries difficult to obtain otherwise. Although a simple and efficient protocol to promote these transformations was developed, the mechanism was not fully unravelled. Herein, after a combination of experimental, spectroscopic and computational studies (using DFT methods) we propose that this isomerization event takes place through a retro-Mannich//Mannich cascade, via the formation of an iminium ion with E geometry. Fil: Gerosa, Gabriela Guillermina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A synthetic strategy has been developed for the preparation of immobilized 1,2-aminoalcohols starting from easily available and renewable chiral building blocks. They were tested as chiral ligands for the asymmetric diethylzinc addition to carbonyl compounds. Enantioselectivities were comparable to those observed for non-immobilized analogs. These results provide strong evidence for the flexibility of our approach to generate highly valuable supported chiral ligands derived from cellulose-rich materials.

Levoglucosenone has been used as template for the synthesis of a wide variety of compounds with an impressive structural variability. However, scarce work has been done regarding the generation of new bioactive entities. Here we report the cytotoxic effect of levoglucosenone and some related derivatives against hepatocarcinoma cell lines. Compounds were obtained in only one synthetic step and one of them showed an activity within the range of IC50values of cisplatin, a frequently administered chemotherapy drug. Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Danielli, Mauro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Fisiología Experimental. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Fisiología Experimental; Argentina Fil: Marinelli, Raul Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Fisiología Experimental. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Fisiología Experimental; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Chiral acrylic esters derived from biomass were developed as models to have a better insight in the aryl-vinyl π-stacking interactions. Quantum chemical calculations, NMR studies and experimental evidences demonstrated the presence of equilibriums of at least four different conformations: π-stacked and face-to-edge, each of them in an s-cis/s-trans conformation. The results show that the stabilization produced by the π-π interaction makes the π-stacked conformation predominant in solution and this stabilization is slightly affected by the electron density of the aromatic counterpart. Fil: Corne, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: De Arellano, Carmen Ramirez. Universidad de Valencia; España Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A series of peripherally carbazole functionalized dendrimeric starburst monomers were synthesized and characterized. The electrochemical polymerization over Pt and indium tin oxide electrodes of fully π-conjugated dendrimers allows the generation of electro-active polymeric films. Dendrimers were design with and without electroactive central core (triphenylamine) connected to peripherals moieties, which influence the physicochemical characteristics of the electrogenerated polymers. The versatile electropolymerization methodology allows the generation of thin films of hyperbranched macromolecules with good electrical conductivity, reversible electrochemical processes and electrochromic properties. Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Minudri, Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Heredia, Daniel Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Fernandez, Luciana Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Otero, Luis Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Fungo, Fernando Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina

An efficient and straightforward synthesis of a novel 3-thiomannoside derivative (1,2,4,6-tetra-O-acetyl-3-S-acetyl-3-thio-β-d-mannopyranoside) was developed starting from levoglucosenone. A xanthate-thiocarbonate exchange under acidic conditions was the key step for the new C-S bond. The product was obtained enantiospecifically in very good overall yield. Fil: Comba, María Betina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Giordano, Enrique David Victor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A synthetic strategy has been developed for the preparation of immobilized 1,2-aminoalcohols starting from easily available and renewable chiral building blocks. They were tested as chiral ligands for the asymmetric diethylzinc addition to carbonyl compounds. Enantioselectivities were comparable to those observed for non-immobilized analogs. These results provide strong evidence for the flexibility of our approach to generate highly valuable supported chiral ligands derived from cellulose-rich materials. Fil: Botta, María Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Biava, Hernan Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Mata, Ernesto Gabino. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Two novel aromatic molecules were synthesized via a modified Ullmann coupling starting from a known compound 2,7-diiodofluorenone with carbazole derivatives. These compounds were obtained in very good yields. Due to their fluorophore components, like fluorenone and carbazole, they could be applied as scaffolds for the development of organic materials like dendrimers and polymers. Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

An experimental and computational study was conducted to assess the effect of chlorine and bromine substitution in Diels–Alder reactions involving chiral α-halo enones as dienophiles. An important rate enhancement was observed in the case of acyclic dienes, while the use of cyclic dienes resulted in prolonged reaction times and lower yields. DFT calculations suggest that these reactions are governed by finely balanced geometric and electronic features at the TSs.

An appealing inversion in the regiochemical outcome of Diels–Alder reactions between levoglucosenone ( 1 ) and its α-bromo derivative ( 5 ) with isoprene ( 2 ) was studied computationally. Based on different DFT calculations we concluded that both reactions should display the same regioselectivity. This result was further validated experimentally.

The Diels-Alder reaction of a pyranose-derived nitroalkene 1 with cyclopentadiene is described, and the unexpected facial selectivity of the cycloaddition is analyzed by a computational study.

Chiral alcohols were designed and easily prepared from levoglucosenone, a biomass-derived valuable synthon. These alcohols were tested as chiral auxiliaries in asymmetric Diels–Alder reactions between the corresponding acrylates with acyclic and cyclic dienes. The regio, stereo, and facial selectivity varied from very good to excellent, depending upon the benzylic substitution of the auxiliary and the diene employed. As a consequence, after removal of the auxiliary, the resulting carboxylic acid derivatives were obtained in 72–99% ee.

The ozonolysis of carbohydrate derived norbornene systems in participating solvents demonstrated that different remote controlling factors could induce the regioselective fragmentation of the primary ozonide. The exo norbornene series afforded a complete regioselective process.

New chiral auxiliaries derived from levoglucosenone were developed in a simple and efficient way and evaluated as chiral inductors in asymmetric Diels–Alder reactions between the corresponding acrylate derivatives and cyclopentadiene. The results showed an important influence of the absolute configuration of the C(2) center of the auxiliary on the level of stereoinduction obtained.

An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity. Fil: Gerosa, Gabriela Guillermina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

The effect of an extra EWG in the reactivity and regioselectivity in Diels?Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically ac-tivated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction. Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

Ozonolysis of a carbohydrate derived norbornene system afforded a stable intramolecular cross-ozonide through a stereocontrolled pathway involving a regioselective fragmentation of the primary ozonide.

The Diels–Alder reaction of the acrylate derived from levoglucosenone with cyclopentadiene was studied under several conditions, in the presence and absence of a Lewis acid. The results showed satisfactory diastereomeric excess and the ratio of cycloadducts was found to depend on the reaction conditions. A reversal in stereoselectivity was observed when EtAlCl 2 or Et 2 AlCl were employed as Lewis acids.

A two-step general approach to a new chiral auxiliary starting from levoglucosenone is reported. The compound is obtained by a [4+2] cycloaddition reaction with anthracene followed by a diastereoselective reduction of the C-2 keto function in high overall yield. The auxiliary has been used as chiral template in an asymmetric Diels–Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene and shown to be efficient for asymmetric induction.

The oxirane ring-opening of an anhydro sugar with diethylaluminum cyanide (Et2AlCN) is a direct approach for obtaining a cyano derivative. Methyl 2,3-anhydro-4,6-O-benzylidene-α- d -allopyranoside showed anomalous chemical behavior when treated with Et2AlCN. The reaction afforded the corresponding β-cyanohydrin as the minor component from a mixture of compounds resulting from the benzylidene acetal ring-opening caused by the attack of ethyl or cyano groups.

The completely regioselective fragmentation of the primary ozonide formed during the ozonolysis of an unsymmetrical substituted norbornene system in the presence of methanol appears to be controlled by remote substituents and affords a tetrasubstituted cyclopentane moiety as a unique product in an almost quantitative yield.

A short and efficient methodology for the synthesis of chiral dioxa-caged Compounds from levoglucose-none, a biomass-derived enone, is herein Presented. The key transformation, that involves a cascade 3-step cationic cyclization, was efficiently carried out in high yields and selectivities by Montmorillonite K-10 catalysis. The usefulness of K-10 in related semi-pinacol rearrangements to obtain pyran-3-ones is also shown. Interesting differences in the reactivity pattern was found for epimeric alcohols, and the origins of these findings were determined by DFT calculations. Fil: Zurita, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Avila, Aylén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

The first application of levoglucosenone-derived chiral auxiliaries in asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides is given.

AM1 and B3LYP calculations were performed for the Diels–Alder reactions of a series of d -glucose-derived dienophiles with cyclopentadiene. The preferred β vs. α diastereofacial addition and exo vs. endo selectivities are explained on the basis of products and transition states stabilities. Computed exo/endo ratios change in the correct direction although they do not agree quantitatively with available experimental data. The relative reactivity of the dienophiles bearing a carbonyl group can be interpreted in terms of FMO theory as well as of repulsive interactions in the corresponding transition states. The calculations fail to explain the observed lack of reactivity for the dienophile bearing a cyano group.

A novel and general approach has been delineated for the enantiomerically pure synthesis of the angularly fused tricyclic system of the pentalenolactone family of compounds. D-Glucose is used as starting material and a diasteroselective Diels-Alder reaction sets the elements for the ring junctions.