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      β-Cyclodextrin coated Fe3O4 nanoparticles: a simple preparation and application for selective oxidation of alcohols in water

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          Abstract

          A magnetically separable catalyst was synthesized via a carbodiimide activation process with β-cyclodextrin functionalized by core-shell nanoparticles (Fe3O4/SiO2/CM-β-CD). The catalyst presented high activity for selective oxidation of various alcohols with NaOCl as oxidant and water only as the solvent. A substrate-selective and transition metal-free process was achieved with easy separation of the catalyst.

          Translated abstract

          Um catalisador magnético foi sintetizado via proceso de ativação da carboimida em β-ciclodextrina funcionalizada com nanopartículas core-shell (Fe3O4/SiO2/CM-β-CD). O catalisador apresenta elevada atividade na oxidação seletiva de vários álcoois usando NaOCl como oxidante e água como solvente. Foi obtido um processo seletivo na ausência de metal de transição e de fácil separação do catalisador.

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          Convergent Synthesis of Diverse Tetrahydropyridines via Rh(I)-Catalyzed C–H Functionalization Sequences

          Tehetena Mesganaw, Jonathan Ellman (2014)
          A Rh-catalyzed C–H bond activation/alkenylation/electrocyclization cascade reaction provides diverse 1,2-dihydropyridines from simple and readily available precursors. The reaction can be carried out at low (<1%) Rh-catalyst loadings, and the use of the robust, air-stable Rh precatalyst, [RhCl(cod)]2, enables the cascade reaction to be easily performed on the benchtop. The 1,2-dihydropyridine products serve as extremely versatile synthetic intermediates for further elaboration often without isolation. The addition of electrophiles under kinetic or thermodynamic conditions provides a wide range of iminiums. Subsequent addition of a nucleophile then generates a diverse array of differently substituted piperidine products. Additionally, [3 + 2] and [4 + 2] cycloadditions of the 1,2-dihydropyridine intermediate provides access to bridged bicyclic structures such as tropanes and isoquinuclidines. These concise reaction sequences enable the formation of highly substituted piperidines in synthetically useful yields with excellent diastereoselectivity.
          Article 0 comments Cited 126 times – based on 0 reviews     Review now
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            Photodynamics and time-resolved fluorescence of azobenzene in solution: a mixed quantum-classical simulation.

            Teresa Cusati, Giovanni Granucci, Maurizio Persico (2011)
            We have simulated the photodynamics of azobenzene by means of the Surface Hopping method. We have considered both the trans → cis and the cis → trans processes, caused by excitation in the n → π* band (S(1) state). To bring out the solvent effects on the excited state dynamics, we have run simulations in four different environments: in vacuo, in n-hexane, in methanol, and in ethylene glycol. Our simulations reproduce very well the measured quantum yields and the time dependence of the intensity and anisotropy of the transient fluorescence. Both the photoisomerization and the S(1) → S(0) internal conversion require the torsion of the N═N double bond, but the N-C bond rotations and the NNC bending vibrations also play a role. In the trans → cis photoconversion the N═N torsional motion and the excited state decay are delayed by increasing the solvent viscosity, while the cis → trans processes are less affected. The analysis of the simulation results allows the experimental observations to be explained in detail, and in particular the counterintuitive increase of the trans → cis quantum yield with viscosity, as well as the relationship between the excited state dynamics and the solvent effects on the fluorescence lifetimes and depolarization.
            Article 0 comments Cited 72 times – based on 0 reviews     Review now
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              Dissecting Anion Effects in Gold(I)-Catalyzed Intermolecular Cycloadditions

              Anna Homs, Carla Obradors-Tarragó, David Leboeuf … (2014)
              From a series of gold complexes of the type [t-BuXPhosAu(MeCN)]X (X=anion), the best results in intermolecular gold(I)-catalyzed reactions are obtained with the complex with the bulky and soft anion BAr4 F− [BAr4 F−=3,5-bis(trifluoromethyl)phenylborate] improving the original protocols by 10–30% yield. A kinetic study on the [2+2] cycloaddition reaction of alkynes with alkenes is consistent with an scenario in which the rate-determining step is the ligand exchange to generate the (η2-phenylacetylene)gold(I) complex. We have studied in detail the subtle differences that can be attributed to the anion in this formation, which result in a substantial decrease in the formation of unproductive σ,π-(alkyne)digold(I) complexes by destabilizing the conjugated acid formed.
              Article 0 comments Cited 60 times – based on 0 reviews     Review now
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                Author and article information

                Contributors
                Jie Zhu: Role: ND
                Peng-cheng Wang: Role: ND
                Ming Lu: Role: ND
                Journal
                Journal ID (publisher): jbchs
                Title: Journal of the Brazilian Chemical Society
                Abbreviated Title: J. Braz. Chem. Soc.
                Publisher: Sociedade Brasileira de Química (São Paulo )
                ISSN: 1678-4790
                Publication date (Print): January 2013
                Volume: 24
                Issue: 1
                Pages: 171-176
                Affiliations
                [1 ] Nanjing University China
                Article
                Publisher ID: S0103-50532013000100021
                DOI: 10.1590/S0103-50532013000100021
                SO-VID: 704846ed-47ab-4546-b5d2-d14508a382c8
                License:

                http://creativecommons.org/licenses/by/4.0/

                History
                Product

                SciELO Brazil

                Self URI (journal page): http://www.scielo.br/scielo.php?script=sci_serial&pid=0103-5053&lng=en
                Categories
                Subject: CHEMISTRY, MULTIDISCIPLINARY

                ScienceOpen disciplines: General chemistry
                Keywords: β-cyclodextrin,magnetic,oxidation
                Data availability:
                ScienceOpen disciplines: General chemistry
                Keywords: β-cyclodextrin, magnetic, oxidation

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