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  • 951.
    Wettergren, Jenny
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Buitrago, Elina
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ryberg, Per
    Adolfsson, Hans
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mechanistic Investigation on the Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Pseudo-Dipeptides Ruthenium complexes2009In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 15, no 23, p. 5709-5718Article in journal (Refereed)
    Abstract [en]

    Lithium-powered: A kinetic investigation into the asymmetric transfer hydrogenation of non-activated aryl alkyl ketones, catalyzed by N-Boc-protected -amino acid hydroxyamide ruthenium–arene complexes, has revealed that the reactions proceed through an unprecedented bimetallic outer-sphere mechanism. Under optimized conditions, these catalysts provide access to secondary alcohols in high yields and with excellent enantioselectivities (>99 % ee).

    The combination of N-Boc-protected -amino acid hydroxyamides (pseudo-dipeptides) and [{Ru(p-cymene)Cl2}2] resulted in the formation of superior catalysts for the asymmetric transfer hydrogenation (ATH) of non-activated aryl alkyl ketones in propan-2-ol. The overall kinetics of the ATH of acetophenone to form 1-phenylethanol in the presence of ruthenium pseudo-dipeptide catalysts were studied, and the individual rate constants for the processes were determined. Addition of lithium chloride to the reaction mixtures had a strong influence on the rates and selectivities of the processes. Kinetic isotope effects (KIEs) for the reduction were determined and the results clearly show that the hydride transfer is rate-determining, whereas no KIEs were detected for the proton transfer. From these observations a novel bimetallic outer-sphere-type mechanism for these ATH process is proposed, in which the bifunctional catalysts mediate the transfer of a hydride and an alkali metal ion between the hydrogen donor and the substrate. Furthermore, the use of a mixture of propan-2-ol and THF (1:1) proved to enhance the rates of the ATH reactions. A series of aryl alkyl ketones were reduced under these conditions in the presence of 0.5 mol % of catalyst, and the corresponding secondary alcohols were formed in high yields and with excellent enantioselectivities (>99 % ee) in short reaction times.

  • 952.
    Wettergren, Jenny
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Buitrago, Elina
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ryberg, Per
    Adolfsson, Hans
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mechanistic investigations into the asymmetric transfer hydrogenation of ketones catalyzed by pseudo-dipeptide ruthenium complexes2009In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 15, no 23, p. 5709-5718Article in journal (Refereed)
  • 953.
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    A perspective on the primary and three-dimensional structures of carbohydrates2013In: Carbohydrate Research, ISSN 0008-6215, E-ISSN 1873-426X, Vol. 378, p. 123-132Article in journal (Refereed)
    Abstract [en]

    Carbohydrates, in more biologically oriented areas referred to as glycans, constitute one of the four groups of biomolecules. The glycans, often present as glycoproteins or glycolipids, form highly complex structures. In mammals ten monosaccharides are utilized in building glycoconjugates in the form of oligo-(up to about a dozen monomers) and polysaccharides. Subsequent modifications and additions create a large number of different compounds. In bacteria, more than a hundred monosaccharides have been reported to be constituents of lipopolysaccharides, capsular polysaccharides, and exopolysaccharides. Thus, the number of polysaccharide structures possible to create is huge. NMR spectroscopy plays an essential part in elucidating the primary structure, that is, monosaccharide identity and ring size, anomeric configuration, linkage position, and sequence, of the sugar residues. The structural studies may also employ computational approaches for NMR chemical shift predictions (CASPER program). Once the components and sequence of sugar residues have been unraveled, the three-dimensional arrangement of the sugar residues relative to each other (conformation), their flexibility (transitions between and populations of conformational states), together with the dynamics (timescales) should be addressed. To shed light on these aspects we have utilized a combination of experimental liquid state NMR techniques together with molecular dynamics simulations. For the latter a molecular mechanics force field such as our CHARMM-based PARM22/SU01 has been used. The experimental NMR parameters acquired are typically H-1, H-1 cross-relaxation rates (related to NOEs), (3)JCH and (3)JCC trans-glycosidic coupling constants and H-1, C-13-and H-1, H-1-residual dipolar couplings. At a glycosidic linkage two torsion angles phi and psi are defined and for 6-substituted residues also the omega torsion angle is required. Major conformers can be identified for which highly populated states are present. Thus, in many cases a well-defined albeit not rigid structure can be identified. However, on longer timescales, oligosaccharides must be considered as highly flexible molecules since also anti-conformations have been shown to exist with H-C-O-C torsion angles of similar to 180 degrees, compared to syn-conformations in which the protons at the carbon atoms forming the glycosidic linkage are in close proximity. The accessible conformational space governs possible interactions with proteins and both minor changes and significant alterations occur for the oligosaccharides in these interaction processes. Transferred NOE NMR experiments give information on the conformation of the glycan ligand when bound to the proteins whereas saturation transfer difference NMR experiments report on the carbohydrate part in contact with the protein. It is anticipated that the subtle differences in conformational preferences for glycan structures facilitate a means to regulate biochemical processes in different environments. Further developments in the analysis of glycan structure and in particular its role in interactions with other molecules, will lead to clarifications of the importance of structure in biochemical regulation processes essential to health and disease.

  • 954.
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Computational and experimental analysis of oligosaccharide conformation and dynamics2011In: Abstracts of Papers, 241st ACS National Meeting & Exposition, Anaheim, CA, United States, March 27-31, 2011, American Chemical Society (ACS), 2011Conference paper (Refereed)
    Abstract [en]

    Carbohydrate structures in the form of glycoconjugates are found in Nature, e.g., as N- and O-linked glycoproteins, glycolipids, short-chain lipopolysaccharides also referred to as lipooligosaccharides and saponins.  The carbohydrate constituent may be studied as part of the glycoconjugate or as oligosaccharides. A number of experimental biophysical techniques are available in order to investigate their conformation and dynamics, in particular, NMR spectroscopy, both in solution and in the solid state, X-ray diffraction on crystals, neutron diffraction with isotopic substitution carried out in the solution state, optical rotation, ultrasonic relaxation and more recently Raman optical activity. Computational approaches including molecular mechanics,1 molecular dynamics simulations,2 ab initio and DFT methods3 may subsequently be employed to study and interpret conformational equilibria based on experimental data. The use of carbon-13 site-specifically synthesized oligosaccharides for obtaining, in particular, conformationally dependent trans-glycosidic homo- and heteronuclear coupling constants and interpretation of conformational equilibria from these based on recently developed Karplus-type relationships for spin-spin coupling constants over three bonds4 will be presented for different oligosaccharides in quest for a description of the population distribution of the torsion angles at the glycosidic linkage.

  • 955. Wieczorek, Birgit
    et al.
    Träff, Annika
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Krumlinde, Patrik
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dijkstra, Harm P.
    Egmond, Maarten R.
    van Koten, Gerard
    Bäckvall, Jan-Erling
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Klein Gebbink, Robertus J. M.
    Covalent anchoring of a racemization catalyst to CALB-beads: towards dual immobilization of DKR catalysts2011In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 52, no 14, p. 1601-1604Article in journal (Refereed)
    Abstract [en]

    The preparation of a heterogeneous bifunctional catalytic system, combining the catalytic properties of an organometallic catalyst (racemization) with those of an enzyme (enantioselective acylation) is described. A novel ruthenium phosphonate inhibitor was synthesized and covalently anchored to a lipase immobilized on a solid support (CALB, Novozym® 435). The immobilized bifunctional catalytic system showed activity in both racemization of (S)-1-phenylethanol and selective acylation of 1-phenylethanol.

  • 956. Wieczorek, Birgit
    et al.
    Träff, Annika
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Krumlinde, Patrik
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dijkstra, Harm P.
    Egmond, Maarten R.
    van Koten, Gerard
    Bäckvall, Jan-Erling
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Klein Gebbink, Robertus J.M.
    Site-Specific Covalent Immobilization of a Racemization Catalyst onto Lipase-containing BeadsManuscript (preprint) (Other academic)
    Abstract [en]

    The synthesis and application of the novel heterogeneous bifunctional catalyst CALB-5 as a racemization and resolution catalyst for the dynamic kinetic resolution is described. The semisynthetic ruthenium lipase hybrid CALB-5 was obtained by inhibiting CALB beads with the novel ruthenium phosphonate complex 5 possessing a lipase active site-directed phosphonate group. By partially inhibiting the lipase beads with 5, a bifunctional catalytic system was obtained. Racemization, by the Ru-catalytic site, gave 0% ee after 24 h, and the kinetic resolution, enzymatic acylation by the uninhibited CALB sites, gave 28% conversion of 1-phenylethanol after 3 h with >99% ee of the acetylated product. A dynamic kinetic resolution experiment of (S)-1-phenylethanol with CALB-5 gave the acylated (R)-product in 18% yield and with >99% ee.

  • 957.
    Wikmark, Ylva
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Engineering Candida antarctica Lipase A for Enantioselective Transformations in Organic Synthesis: Design, Immobilization and Organic Solvent Screening of Smart Enzyme Libraries2015Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    The use of enzymes as catalysts in organic synthesis constitutes an attractive alternative to conventional chemical catalysis. Enzymes are non-toxic and biodegradable and they can operate under mild reaction conditions. Furthermore, they often display high chemo-, regio- and stereoselectivity, enabling specific reactions with single product outcome.

    By the use of protein engineering, enzymes can be altered for the specific needs of the researcher. The major part of this thesis describes engineering of lipase A from Candida antarctica (CalA), for improved enantioselectivity in organic synthetic transformations.

    The first part of the thesis describes a highly combinatorial method for the introduction of mutation sites in an enzyme library. By the simultaneous introduction of nine mutations, we found an enzyme variant with five out of the nine possible mutations. This quintuple variant had an enlarged active site pocket and was enantioselective and active for our model substrate, an ibuprofen ester. This is a bulky substrate for which the wild-type enzyme shows no enantioselectivity and very poor activity.

    In the second part of the thesis, we continued our approach of combinatorial, focused enzyme libraries. This time we aimed at decreasing the alcohol pocket of CalA, in order to increase the enantioselectivity for small and medium-sized secondary alcohols. The enzyme library was bound on microtiter plates and screened by a transacylation reaction in organic solvent. This library yielded an enzyme variant with high enantioselectivity for the model substrate 1-phenyl ethanol, and high to excellent selectivity for other alcohols tested. Screening in organic solvent is advantageous since a potential hit is more synthetically useful.

    In the third part of the thesis, we used manipulated beads of controlled porosity glass (EziG™) for enzyme immobilization, and demonstrated the generality of this carrier for several enzyme classes. EziG™ allowed fast enzyme immobilization with simultaneous purification and yielded active biocatalysts in all cases.

    The last project describes the function of the proposed active site flap in CalA. In our study, we removed this motif. The engineered variant was compared to the wild-type enzyme by testing the amount of interfacial activation and the selectivity for certain alcohols. We showed that the motif is indeed controlling the entrance to the active site and that the flap is not part of the enantioselectivity determining machinery. 

  • 958.
    Wikmark, Ylva
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Engelmark Cassimjee, Karim
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Lihammar, Richard
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Removing the Active-Site Flap in Lipase A from Candida antarctica Produces a Functional Enzyme without Interfacial Activation2016In: ChemBioChem (Print), ISSN 1439-4227, E-ISSN 1439-7633, Vol. 17, no 2, p. 141-145Article in journal (Refereed)
    Abstract [en]

    A mobile region is proposed to be a flap that covers the active site of Candida antarctica lipase A. Removal of the mobile region retains the functional properties of the enzyme. Interestingly interfacial activation, required for the wild-type enzyme, was not observed for the truncated variant, although stability, activity, and stereoselectivity were very similar for the wild-type and variant enzymes. The variant followed classical Michaelis-Menten kinetics, unlike the wild type. Both gave the same relative specificity in the transacylation of a primary and a secondary alcohol in organic solvent. Furthermore, both showed the same enantioselectivity in transacylation of alcohols and the hydrolysis of alcohol esters, as well as in the hydrolysis of esters chiral at the acid part.

  • 959.
    Wikmark, Ylva
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Humble, Maria Svedendahl
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Combinatorial Library Based Engineering of Candida antarctica Lipase A for Enantioselective Transacylation of sec-Alcohols in Organic Solvent2015In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 54, no 14, p. 4284-4288Article in journal (Refereed)
    Abstract [en]

    A method for determining lipase enantioselectivity in the transacylation of sec-alcohols in organic solvent was developed. The method was applied to a model library of Candida antarctica lipase A (CalA) variants for improved enantioselectivity (E values) in the kinetic resolution of 1-phenylethanol in isooctane. A focused combinatorial gene library simultaneously targeting seven positions in the enzyme active site was designed. Enzyme variants were immobilized on nickel-coated 96-well microtiter plates through a histidine tag (His6 -tag), screened for transacylation of 1-phenylethanol in isooctane, and analyzed by GC. The highest enantioselectivity was shown by the double mutant Y93L/L367I. This enzyme variant gave an E value of 100 (R), which is a dramatic improvement on the wild-type CalA (E=3). This variant also showed high to excellent enantioselectivity for other secondary alcohols tested.

  • 960.
    Willy, Benjamin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Szabó, Kálmán J
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Development of pincer complex-catalyzed oxidative C-H activation borylation reactions: Synthetic applications and mechanistic studies2010In: Abstracts of Papers, 239th ACS National Meeting, San Francisco, CA, United States, March 21-25, 2010, Washington D C: American Chemical Society , 2010Conference paper (Other academic)
  • 961.
    Winnberg, Ulrika
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Environmental Chemistry.
    Rydén, Andreas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Environmental Chemistry.
    Löfstrand, Karin
    Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
    Asplund, Lillemor
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Environmental Chemistry.
    Bignert, Anders
    Marsh, Göran
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Environmental Chemistry.
    Novel Octabrominated Phenolic Diphenyl Ether Identified in Blue Mussels from the Swedish West Coast2014In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 48, no 6, p. 3319-3326Article in journal (Refereed)
    Abstract [en]

    Hydroxylated (OH−) and methoxylated (MeO−) polybrominated diphenyl ethers (PBDEs) are compounds present in the marine environment and OH–PBDEs are of toxicological concern and are therefore of interest to monitor in the environment. A phenolic octaBDE was tentatively identified in the phenolic fraction of previously analyzed mussel samples after methylation of the halogenated phenolic compounds (HPCs). The aim of the present study was to confirm the identity of this compound in blue mussels and investigate whether the analyte is diOH– and/or OH–MeO–octaBDE. Two reference standards, 6,6′-dimethoxy-2,2′,3,3′,4,4′,5,5′-octabromodiphenyl ether (6,6′-diMeO–BDE194) and 6-ethoxy-6′-methoxy-2,2′,3,3′,4,4′,5,5′-octabromodiphenyl ether (6-EtO-6′-MeO–BDE194) were prepared via O-arylation of 2,3,4,5-tetrabromo-6-methoxyphenol and 2,3,4,5-tetrabromo-6-ethoxyphenol, respectively, with a novel unsymmetrical diaryliodonium salt, 2,3,4,5-tetrabromo-6-methoxydiphenyliodonium triflate. The GC retention time and GC/MS spectrum of the synthesized 6,6′-diMeO–BDE194 correspond well with the analyte in the methylated phenolic fraction of a mussel extract from a previous study. Structural analysis performed in this study indicate that the synthesized 6,6′-diMeO–BDE194 and 6-EtO-6′-MeO–BDE194 correspond well with 6-hydroxy-6′-methoxy-2,2′,3,3′,4,4′,5,5′-octabromodiphenyl ether (6-OH–6′-MeO–BDE194) after methylation and ethylation, respectively, of the HPCs in the mussel extracts. The compound 6-OH–6′-MeO–BDE194 was identified and quantified in new mussels, sampled in 2012 from two locations on the Swedish west coast, with geometric mean concentrations of 3700 and 410 ng/g fat, respectively.

  • 962.
    Winqvist, Anna
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Studies towards a method for incorporation of 3'-deoxy-3'-C-methylenephosphonate linkages into oligonucleotides2002Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Synthetic strategies towards 3’-deoxy-3’-C-methylenephosphinate building blocks were explored. The key transformations involved stereoselective hydroboration of 1-[2-O-(tert-butyldimethylsilyl-5-O-(4-methoxytrityl)-3-deoxy-3-C-methylene- ß -D-erythro-pentofuranosyl]uracil to give the corresponding 3’-deoxy-3’-C- hydroxymethyl derivative with ribo-configuration, as well as the further conversion into a precursor with a suitable leaving group, e. g., triflate, for subsequent substitution with the phosphinic acid synthon bis(trimethylsilyl)hypophosphite. Improvements of these steps enabled synthesis of 2’-O-(tert-butyldimethylsilyl-5’-O-( 4-methoxytrityl)-3’-deoxy-3’-C-methylenephosphinate uridine in a respectable overall yield of 40% over 6 steps, from the corresponding 2’-O-(tert-butyldimethylsilyl- 5’-O-(4-methoxytrityl)uridine.

    For the introduction of internucleosidic 3’-deoxy-3’-C-methylenephosphonate linkages into oligonucleotides, a preparatory study of the elongation steps, i. e., coupling of the phosphinate building block to the 5’-hydroxyl function of a nucleoside derivative and subsequent oxidation, was performed. Of several coupling reagents studied for the activation of the phosphinate building block prior to coupling, the most promising proved to be N,N-bis(2-oxo-3-oxazolidin-1-yl)phosphinic chloride. The oxidation of the resulting 3’-deoxy-3’-C-methylenephosphinate ester to the corresponding 3’-deoxy-3’-C-methylenephosphonate linkage was achieved using iodine in pyridine-water, in the presence of a catalyst, i. e., either a base (triethylamine) or an acid (pyridinium salt).

  • 963.
    Wolpher, Henriette
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ruthenium(II) Polypyridyl Complexes in Supramolecular Systems relevant to Artificial Photosynthesis2005Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis describes the synthesis and properties of ruthenium complexes relevant to artificial photosynthesis. The work includes preparation of RuIIpolypyridine complexes as well as multi component systems where RuII(bpy)3 or RuII(tpy)2 type complexes are used as photosesnsitizers.

    In the first part, the synthesis and characterisation of bipyridyl(pyridyl)methane type ligands and the corresponding ruthenium(II) bistridentate polypyridyl complexes is described. The bipyridyl-pyridyl methane type ligands were designed to increase the excited state lifetime of ruthenium(II) bisterpyridine-type complexes by altering the ligand field as compared to normal terpyridine ligands.

    In the second part photoinduced electron transfer and formation of charge separated states in donor-photosensitizer dyads or donor-photosensitizer-acceptor triads is studied. The first covalently linked donor-photosensitizer-acceptor triad with tyrosine as electron donor was prepared, and long lived light induced charge separation was observed. RuIIterpyridine complexes linked to carotenoid or tyrosine were also prepared, for studies of light induced charge separation on a TiO2 surface. Tryptofan was covalently linked to Ru(bpy)3 and proton coupled electron transfer from tryptophan to photogenerated ruthenium(III) was demonstrated. A pH-dependent study of the electron transfer rate gave insight into the mechanism of proton coupled electron transfer in amino acids.

    Finally, the last part of the thesis presents the preparation and properties of the first complex containing a photosensitizer covalently linked to a Fe-hydrogenase active site model.

  • 964. Wu, Emilia L.
    et al.
    Fleming, Patrick J.
    Yeom, Min Sun
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Klauda, Jeffery B.
    Fleming, Karen G.
    Im, Wonpil
    E. coil Outer Membrane and Interactions with OmpLA2014In: Biophysical Journal, ISSN 0006-3495, E-ISSN 1542-0086, Vol. 106, no 11, p. 2493-2502Article in journal (Refereed)
    Abstract [en]

    The outer membrane of Gram-negative bacteria is a unique asymmetric lipid bilayer composed of phospholipids (PLs) in the inner leaflet and lipopolysaccharides (LPSs) in the outer leaflet. Its function as a selective barrier is crucial for the survival of bacteria in many distinct environments, and it also renders Gram-negative bacteria more resistant to antibiotics than their Gram-positive counterparts. Here, we report the structural properties of a model of the Escherichia coli outer membrane and its interaction with outer membrane phospholipase A (OmpLA) utilizing molecular dynamics simulations. Our results reveal that given the lipid composition used here, the hydrophobic thickness of the outer membrane is similar to 3 angstrom thinner than the corresponding PL bilayer, mainly because of the thinner LPS leaflet. Further thinning in the vicinity of OmpLA is observed due to hydrophobic matching. The particular shape of the OmpLA barrel induces various interactions between LPS and PL leaflets, resulting in asymmetric thinning around the protein. The interaction between OmpLA extracellular loops and LPS (headgroups and core oligosaccharides) stabilizes the loop conformation with reduced dynamics, which leads to secondary structure variation and loop displacement compared to that in a DLPC bilayer. In addition, we demonstrate that the LPS/PL ratios in asymmetric bilayers can be reliably estimated by the per-lipid surface area of each lipid type, and there is no statistical difference in the overall membrane structure for the outer membranes with one more or less LPS in the outer leaflet, although individual lipid properties vary slightly.

  • 965. Wångsell, Fredrik
    et al.
    Russo, Francesco
    Sävmarker, Jonas
    Åsa, Rosenquist
    Samuelsson, Bertil
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Larhed, Mats
    Design and synthesis of BACE-1 inhibitors utilizing a tertiary hydroxyl motif as the transition state mimic2009In: Bioorganic & Medicinal Chemistry Letters, ISSN 0960-894X, Vol. 19, no 16, p. 4711-4714Article in journal (Refereed)
  • 966.
    Xu, Chao
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Afewerki, Samson
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Córdova, Armando
    Hedin, Niklas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    A Cyclopalladated Microporous Azo-linked Polymer as a Heterogeneous Catalyst for Eco-friendly Suzuki and Heck Coupling ReactionsManuscript (preprint) (Other academic)
  • 967.
    Xu, Quan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kerdphon, Sutthichat
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Andersson, Pher G.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    C-C Coupling of Ketones with Methanol Catalyzed by a N-Heterocyclic Carbene-Phosphine Iridium Complex2015In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, p. 3576-3579Article in journal (Refereed)
    Abstract [en]

    An N-heterocyclic carbene–phosphine iridium complex system was found to be a very efficient catalyst for the methylation of ketone via a hydrogen transfer reaction. Mild conditions together with low catalyst loading (1 mol %) were used for a tandem process which involves the dehydrogenation of methanol, CC bond formation with a ketone, and hydrogenation of the new generated double bond by iridium hydride to give the alkylated product. Using this iridium catalyst system, a number of branched ketones were synthesized with good to excellent conversions and yields.

  • 968.
    Xu, Quan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kerdphon, Sutthichat
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Rujirawanich, Janjira
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Krajangsri, Suppachai
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Andersson, Pher
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Highly Active Cationic NHC, Phosphine Iridium Catalysts for Base Free Asymmetric Hydrogenation of KetonesManuscript (preprint) (Other academic)
  • 969.
    Xu, Yunhua
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Synthesis and Photoinduced Electron Transfer of Donor-Sensitizer-Acceptor Systems2005Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Artificial systems involving water oxidation and solar cells are promising ways for the conversion of solar energy into fuels and electricity. These systems usually consist of a photosensitizer, an electron donor and / or an electron acceptor. This thesis deals with the synthesis and photoinduced electron transfer of several donor-sensitizer-acceptor supramolecular systems.

    The first part of this thesis describes the synthesis and properties of two novel dinuclear ruthenium complexes as electron donors to mimic the donor side reaction of Photosystem II. These two Ru2 complexes were then covalently linked to ruthenium trisbipyridine and the properties of the resulting trinuclear complexes were studied by cyclic voltammetry and transient absorption spectroscopy.

    The second part presents the synthesis and photoinduced electron transfer of covalently linked donor-sensitizer supramolecular systems in the presence of TiO2 as electron acceptors. Electron donors are tyrosine, phenol and their derivatives, and dinuclear ruthenium complexes. Intramolecular electron transfer from the donor to the oxidized sensitizer was observed by transient absorption spectroscopy after light excitation of the Ru(bpy)32+ moiety. The potential applications of Ru2-based electron donors in artificial systems for water oxidation and solar cells are discussed.

    In the final part, the photoinduced interfacial electron transfer in the systems based on carotenoids and TiO2 is studied. Carotenoids are shown to act as both sensitizers and electron donors, which could be used in artificial systems to mimic the electron transfer chain in natural photosynthesis.

  • 970. Xu, Yunhua
    et al.
    Duan, Lele
    Tong, Lianpeng
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sun, Licheng
    Visible light-driven water oxidation catalyzed by a highly efficient dinuclear ruthenium complex2010In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 46, no 35, p. 6506-6508Article in journal (Refereed)
  • 971.
    Xu, Yunhua
    et al.
    Royal Institute of Technology (KTH).
    Duan, Lele
    Royal Institute of Technology (KTH).
    Åkermark, Torbjörn
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Tong, Lianpeng
    Royal Institute of Technology (KTH).
    Lee, Bao-Lin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Zhang, Rong
    Dalian University of Technology (DUT), (P.R. China).
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sun, Licheng
    Royal Institute of Technology (KTH), Department of Organic Chemistry.
    Synthesis and catalytic water oxidation activities of ruthenium complexes containing neutral ligands2011In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 34, p. 9520-9528Article in journal (Refereed)
    Abstract [en]

    Two dinuclear and one mononuclear ruthenium complexes containing neutral polypyridyl ligands have been synthesised as pre-water oxidation catalysts and characterised by 1H and 13C NMR spectroscopy and ESI-MS. Their catalytic water oxidation properties in the presence of [Ce-(NH4)2(NO3)6] (CeIV) as oxidant at pH 1.0 have been investigated. At low concentrations of CeIV (5 mM), high turnover numbers of up to 4500 have been achieved. An 18O-labelling experiment established that both O atoms in the evolved O2 originate from water. Combined electrochemical study and electrospray ionisation mass spectrometric analysis suggest that ligand exchange between coordinated 4-picoline and free water produces Ru aquo species as the real water oxidation catalysts.

  • 972. Xu, Yunhua
    et al.
    Fischer, Andreas
    Duan, Lele
    Tong, Lianpeng
    Gabrielsson, Erik
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sun, Licheng
    Chemical and light-driven oxidation of water catalyzed by an efficient dinuclear ruthenium complex2010In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 49, no 47, p. 8934-8937Article in journal (Refereed)
  • 973.
    Yang, Bin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Catalytic Stereoselective Formation of C–O, C–C and C–B Bonds: A Voyage from Asymmetric Reactions Enabled by Lipases to Stereoselective Palladium-Catalyzed Oxidative Transformations of Enallenes2017Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis has been focused on enzymatic kinetic resolutions and stereoselective oxidative transformations of enallenes catalyzed by PdII.

    In the first part of the thesis, a detailed discussion on Candida antarctica lipase B (CALB)-catalyzed kinetic resolution (KR) of δ-functionalized alkan-2-acetates is shown. We gained a deeper insight into the mechanism of enzyme-substrate recognition. Changing from an anhydrous solvent to water or a water-containing organic solvent enhanced the enantioselectivity. The effect of –OH was also confirmed by a lipase mutant suggesting that the water molecule mentioned above can be partly mimicked.

    In the second part of the thesis, we developed an efficient KR for allenic alcohols. On this basis, a novel synthesis of optically pure 2-substituted 2,3-dihydrofurans from allenic alcohols via a Ru-catalyzed cycloisomerization was reported. The developed protocol enabled us to assemble an optically pure precursor for total synthesis with three chiral centers from readily available allenol in 2 days.

    In the third part, we reported a class of reactions involving C–H cleavage under mild conditions: PdII-catalyzed oxidative transformations of enallenes. These reactions are particularly attractive since a number of meticulous structures have been achieved from readily accessible starting materials. The directing effect of an unsaturated hydrocarbon was found to be key for these transformations.

    In the final part, we developed the carbonylative insertion reaction discussed in the third part of the thesis into an asymmetric version. By using this methodology, a number of cyclopentenone compounds were obtained in good to excellent enantioselectivity.

  • 974.
    Yang, Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Lihammar, Richard
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-Erling
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Investigation of the Impact of Water on the Enantioselectivity Displayed by CALB in the Kinetic Resolution of δ-Functionalized Alkan-2-ol Derivatives2014In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 42, p. 13517-13521Article in journal (Refereed)
    Abstract [en]

    It is shown that the low enantioselectivity of Candida antarctica lipase B (CALB)-catalyzed transesterification of a δ-functionalized alkan-2-ol to its acetate does not correlate at all with the high enantioselectivity of the CALB-catalyzed hydrolysis of the corresponding acetate in water. This lack of correlation is unusual and for unfunctionalized alkan-2-ol derivatives there is a very good correlation between the enantioselectivity of transesterification of the alcohol and hydrolysis of the corresponding acetate (E>200 in both cases). The results confirm previous predictions from molecular modeling. The water effect was mimicked by CALB variant Ala281Ser, which showed an enhanced enantioselectivity in transesterification of δ-functionalized alkan-2-ols compared to wild-type CALB.

  • 975.
    Yang, Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Qiu, Youai
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Control of Selectivity in Palladium(II)-Catalyzed Oxidative Transformations of Allenes2018In: Accounts of Chemical Research, ISSN 0001-4842, E-ISSN 1520-4898, Vol. 51, no 6, p. 1520-1531Article, review/survey (Refereed)
    Abstract [en]

    Oxidation reactions play a central role in organic synthesis, and it is highly desirable that these reactions are mild and occur under catalytic conditions. In Nature, oxidation reactions occur under mild conditions via cascade processes, and furthermore, they often occur in an enantioselective manner with many of them involving molecular oxygen or hydrogen peroxide as the terminal oxidant. Inspired by the reactions in Nature, we have developed a number of Pd(II)-catalyzed cascade reactions under mild oxidative conditions. These reactions have an intrinsic advantage of step economy and rely on selectivity control in each step. In this Account, we will discuss the control of chemo-, regio-, and diastereoselectivity in Pd(II)-catalyzed dehydrogenative cascade coupling reactions. The enantioselective version of this methodology has also been addressed, and new chiral centers have been introduced using a catalytic amount of a chiral phosphoric acid (CPA). Research on this topic has provided access to important compounds attractive for synthetic and pharmaceutical chemists. These compounds include carbocyclic, heterocyclic, and polycyclic systems, as well as polyunsaturated open-chain structures. Reactions leading to these compounds are initiated by coordination of an allene and an unsaturated pi-bond moiety, such as olefin, alkyne, or another allene, to the Pd(II) center, followed by allene attack involving a C(sp(3))-H cleavage under mild reaction conditions. Recent progress within our research group has shown that weakly coordinating groups (e.g., hydroxyl, alkoxide, or ketone) could also initiate the allene attack on Pd(II), which is essential for the oxidative carbocyclization. Furthermore, a highly selective palladium-catalyzed allenic C(sp(3))-H bond oxidation of allenes in the absence of an assisting group was developed, which provides a novel and straightforward synthesis of [3]dendralene derivatives. For the oxidative systems, benzoquinone (BQ) and its derivatives are commonly used as oxidants or catalytic co-oxidants (electron transfer mediators, ETMs) together with molecular oxygen. A variety of transformations including carbocyclization, acetoxylation, arylation, carbonylation, borylation, beta-hydride elimination, alkynylation, alkoxylation, and olefination have been demonstrated to be compatible with this Pd(II)-based catalytic oxidative system. Recently, several challenging synthetic targets, such as cyclobutenes, seven-membered ring carbocycles, spirocyclic derivatives, functional cyclohexenes, and chiral cyclopentenone derivatives were obtained with high selectivity using these methods. The mechanisms of the reactions were mainly studied by kinetic isotope effects (KIEs) or DFT computations, which showed that in most cases the C(sp(3))-H cleavage is the rate-determining step (RDS) or partially RDS. This Account will describe our efforts toward the development of highly selective and atom-economic palladium(II)-catalyzed oxidative transformation of allenes (including enallenes, dienallenes, bisallenes, allenynes, simple allenes, and allenols) with a focus on overcoming the selectivity problem during the reactions.

  • 976.
    Yang, Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Qiu, Youai
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Jiang, Tuo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Wulff, William D.
    Yin, Xiaopeng
    Zhu, Can
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Enantioselective Palladium-Catalyzed Carbonylative Carbocyclization of Enallenes via Cross-Dehydrogenative Coupling with Terminal Alkyne: Efficient Construction of a-Chirality of Ketones2017In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 56, no 16, p. 4535-4539Article in journal (Refereed)
    Abstract [en]

    An enantioselective PdII/Brønsted acid-catalyzed carbonylative carbocyclization of enallenes ending with a cross-dehydrogenative coupling (CDC) with a terminal alkyne was developed. VAPOL phosphoric acid was found as the best co-catalyst among the examined 28 chiral acids, for inducing the enantioselectivity of α-chiral ketones. As a result, a number of chiral cyclopentenones were easily synthesized in good to excellent enantiomeric ratio with good yields.

  • 977.
    Yang, Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Zhu, Can
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Qiu, Youai
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Enzyme- and Ruthenium-Catalyzed Enantioselective Transformation of alpha-Allenic Alcohols into 2,3-Dihydrofurans2016In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 55, no 18, p. 5568-5572Article in journal (Refereed)
    Abstract [en]

    An efficient one-pot method for the enzyme- and ruthenium-catalyzed enantioselective transformation of alpha-allenic alcohols into 2,3-dihydrofurans has been developed. The method involves an enzymatic kinetic resolution and a subsequent ruthenium-catalyzed cycloisomerization, which provides 2,3-dihydrofurans with excellent enantioselectivity (up to >99%ee). A ruthenium carbene species was proposed as a key intermediate in the cycloisomerization.

  • 978.
    Yang, Hai-Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pathipati, Stalin R.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Selander, Nicklas
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Nickel-Catalyzed 1,2-Aminoarylation of Oxime Ester-Tethered Alkenes with Boronic Acids2017In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 7, no 12, p. 8441-8445Article in journal (Refereed)
    Abstract [en]

    A nickel-catalyzed 1,2-aminoarylation of oximeester-tethered alkenes with boronic acids was developed. A variety of pyrroline derivatives were synthesized in good yields via the successive formation of C(sp(3))-N and C(sp(3))-C(sp(2)) bonds. For cyclobutanone-derived oxime esters, the reaction provided aliphatic nitriles incorporating an aromatic group in the gamma-position. A mechanism involving iminyl radical and carbon-centered radical intermediates was proposed.

  • 979.
    Yang, Hai-Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Selander, Nicklas
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    A redox-economical synthesis of trifluoromethylated enamides with the Langlois reagent2017In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 15, no 8, p. 1771-1775Article in journal (Refereed)
    Abstract [en]

    A redox-economical strategy for the synthesis of trifluoromethylated enamides using copper catalysis is reported. The reaction employs the inexpensive Langlois reagent (CF3SO2Na) and takes place without the need of an external oxidant. The trifluoromethylated enamide products can easily be converted into the corresponding ketone, saturated amide or oxazole.

  • 980.
    Yang, Hai-Bin
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Selander, Nicklas
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Divergent Iron-Catalyzed Coupling of O-Acyloximes with Silyl Enol Ethers2017In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 8, p. 1779-1783Article in journal (Refereed)
    Abstract [en]

    An iron-catalyzed coupling reaction of O-acyloximes and O-benzoyl amidoximes with silyl enol ethers is reported. The protocol provides access to functionalized pyrroles, 1,6-ketonitriles, pyrrolines and imidazolines via carbon-centered radicals generated from an initially formed iminyl radical. The intramolecular cyclization and ring-opening processes of the iminyl radical take place preferentially over reactions that proceed through a 1,3-hydrogen transfer, providing insights into iron-catalyzed reactions with oxime derivatives. The cheap and environmentally friendly iron catalyst, the broad substrate scope and the functional group compatibility make this protocol useful for synthesis of valuable nitrogen-containing products.

  • 981. Yang, Mingjun
    et al.
    Angles d'Ortoli, Thibault
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Säwén, Elin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Jana, Madhurima
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    MacKerell, Jr., Alexander D.
    Delineating the conformational flexibility of trisaccharides from NMR spectroscopy experiments and computer simulations2016In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 18, no 28, p. 18776-18794Article in journal (Refereed)
    Abstract [en]

    The conformation of saccharides in solution is challenging to characterize in the context of a single well-defined three-dimensional structure. Instead, they are better represented by an ensemble of conformations associated with their structural diversity and flexibility. In this study, we delineate the conformational heterogeneity of five trisaccharides via a combination of experimental and computational techniques. Experimental NMR measurements target conformationally sensitive parameters, including J couplings and effective distances around the glycosidic linkages, while the computational simulations apply the well-calibrated additive CHARMM carbohydrate force field in combination with efficient enhanced sampling molecular dynamics simulation methods. Analysis of conformational heterogeneity is performed based on sampling of discreet states as defined by dihedral angles, on root-mean-square differences of Cartesian coordinates and on the extent of volume sampled. Conformational clustering, based on the glycosidic linkage dihedral angles, shows that accounting for the full range of sampled conformations is required to reproduce the experimental data, emphasizing the utility of the molecular simulations in obtaining an atomic detailed description of the conformational properties of the saccharides. Results show the presence of differential conformational preferences as a function of primary sequence and glycosidic linkage types. Significant differences in conformational ensembles associated with the anomeric configuration of a single glycosidic linkage reinforce the impact of such changes on the conformational properties of carbohydrates. The present structural insights of the studied trisaccharides represent a foundation for understanding the range of conformations adopted in larger oligosaccharides and how these molecules encode their conformational heterogeneity into the monosaccharide sequence.

  • 982.
    Yang, Yuzhu
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Szabó, Kálmán J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Synthesis of Allenes by Catalytic Coupling of Propargyl Carbonates with Aryl Iodides in the Presence of Diboron Species2016In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 81, no 1, p. 250-255Article in journal (Refereed)
    Abstract [en]

    Bimetallic copper-/palladium-catalyzed multicomponent reaction of propargyl carbonates, aryl iodides, and diboron species was studied. This procedure can be used for synthesis of di-, tri-, and tetra-substituted allenes. Using diboronic acid, the reaction is supposed to proceed via allenylboronic acid intermediate.

  • 983. Yotapan, Nattawut
    et al.
    Paptchikhine, Alexander
    Bera, Milan
    Avula, Satya Kumar
    Vilaivan, Tirayut
    Andersson, Pher G.
    Stockholm University, Faculty of Science, Department of Organic Chemistry. University of Kwazulu Natal, South Africa.
    Simple Proline-Derived Phosphine-Thiazole Iridium Complexes for Asymmetric Hydrogenation of Trisubstituted Olefins2013In: Asian Journal of Organic Chemistry, ISSN 2193-5807, Vol. 2, no 8, p. 674-680Article in journal (Refereed)
    Abstract [en]

    Proline-based phosphine-thiazole/imidazole ligands have been synthesized and successfully applied in the homogeneous, iridium-catalyzed, asymmetric hydrogenation of trisubstituted functionalized and unfunctionalized olefins. Five different sets of ligands were prepared then evaluated for their catalytic activity and enantioselectivity in asymmetric hydrogenation.

  • 984.
    Yu, Zheng-Bao
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Han, Yu
    Zhao, Lan
    Huang, Shiliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zheng, Qi-Yu
    Lin, Shuangzheng
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Córdova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Intergrown New Zeolite Beta Polymorphs with Interconnected 12-Ring Channels Solved by Combining Electron Crystallography and Single-Crystal X-ray Diffraction2012In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 24, no 19, p. 3701-3706Article in journal (Refereed)
    Abstract [en]

    Two new polymorphs of zeolite beta, denoted as SU-78A and SU-78B, were synthesized by employing dicyclohexylammonium hydroxides as organic structuredirecting agents. The structure was solved by combining transmission electron microscopy and single-crystal X-ray diffraction. SU-78 is an intergrowth of SU-78A and SU-78B and contains interconnected 12-ring channels in three directions. The two polymorphs are built from the same building layer, similar to that for the zeolite beta family. The layer stacking in SU-78, however, is different from those in zeolite beta polymorph A, B, and C, showing new zeolite framework topologies. SU-78 is thermally stable up to 600°C.

  • 985.
    Yuan, Ning
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Swedish University of Agricultural Sciences, Sweden.
    Pascanu, Vlad
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Huang, Zhehao
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Heidenreich, Niclas
    Leubner, Sebastian
    Inge, A. Ken
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Gaar, Jakob
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Stock, Norbert
    Persson, Ingmar
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Probing the active catalytic species generated from Pd(II)@MIL-101-NH2 in Heck coupling reactions: An operando X-ray absorption spectroscopy studyArticle in journal (Refereed)
  • 986.
    Yuan, Weiming
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Szabo, Kalman J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Catalytic Intramolecular Aminofluorination, Oxyfluorination, and Carbofluorination with a Stable and Versatile Hypervalent Fluoroiodine Reagent2015In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 54, no 29, p. 8533-8537Article in journal (Refereed)
    Abstract [en]

    Application of a fluoroiodine analogue of the Togni reagent was studied in fluorocyclization reactions. In the presence of a transition-metal catalyst the applied fluoroiodine reagent can be used for aminofluorination, oxyfluorination, and carbofluorination reactions. The described procedure has a very broad synthetic scope for preparation of functionalized hetero- and isocyclic compounds having a tertiary fluorine substituent.

  • 987.
    Yuan, Weiming
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Szabo, Kalman J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Rhodium-Catalyzed Oxy-Aminofluorination of Diazoketones with Tetrahydrofurans and N-Fluorobenzenesulfonimide2016In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 6, no 10, p. 6687-6691Article in journal (Refereed)
    Abstract [en]

    We have developed a rhodium-catalyzed oxy-aminofluorination method for transformation of diazoketones. The reaction is based on addition of tetrahydrofuran derivatives and N-fluorobenzenesulfonimide (NFSI) to the diazoketone substrate. The reaction can be performed under mild conditions with high regioselectivity. The synthetic scope involves a wide variety of diazoketones and tetrahydrofuran derivatives. The reaction is supposed to proceed via a tetrahydrofuran based onium ylide intermediate, which is formed from rhodium-carbenoid.

  • 988.
    Zaccheus, Mona
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Structural and Conformational Studies of Oligo- and Polysaccharides2012Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    The focus of this thesis is to examine the structural properties of polysaccharides produced by bacteria, as well as the dynamic and conformational behavior of a synthetically derived oligosaccharide.

    The primary structures of the O-polysaccharide repeating units of four different Escherichia coli (E. coli) strains, namely O175, O177, O103 and TD2158, as well as the first report of a capsular polysaccharide produced by lactic acid bacteria Leuconostoc mesenteroides ssp. cremoris PIA2 are reported in paper I–V. Structural analyses have been performed using a combination of nuclear magnetic resonance spectroscopy and chemical component analysis.

    The elucidated structures in paper I–III, as well as paper V, are composed of linear repeating units of varying composition and length. In paper IV, the structure of the O-polysaccharide repeating unit of E. coli TD2158 is determined to be a branched hexasaccharide structure with a heterogeneous substitution pattern, with either a β-GlcpNAc or β-Glcp residue branching to the backbone chain. Incubation with bacteriophage HK620 tailspike protein shows that the polysaccharide is selectively cleaved at the α-GlcpNAc-(1→2)-α-Rhap-linkage of the backbone chain, yielding a 9:1 ratio of β-GlcpNAc/β-Glcp containing hexasaccharides after digestion.

    In paper VI the conformational properties of a trisaccharide, which constitutes an internal epitope of the LeaLex hexasaccharide over-expressed on the surface of squamous lung cancer cells, have been analyzed using NMR spectroscopy and molecular dynamics simulations. The β-(1→3)-linkage of the trisaccharide was shown to be highly flexible.

  • 989.
    Zaccheus, Mona
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pendrill, Robert
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Jackson, Trudy A.
    Wang, An
    Auzanneau, France-Isabelle
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Conformational Dynamics of a Central Trisaccharide Fragment of the LeaLex Tumor Associated Antigen Studied by NMR Spectroscopy and Molecular Dynamics Simulations2012In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 25, p. 4705-4715Article in journal (Refereed)
    Abstract [en]

    Certain carbohydrate structures are recognized as cancer antigens, and identification of these and relevant epitopes are essential in fighting the disease. The trisaccharide beta-D-GlcpNAc-(1?3)-beta-D-Galp-(1?4)-beta-D-GlcpNAc-OMe represents a model for the central region of the LeaLex hexasaccharide and it has herein been investigated by 1D 1H,1H-NOESY experiments to obtain effective interresidue protonproton distances as well as by 2D J-HMBC experiments to determine transglycosidic 3JCH coupling constants. Molecular dynamics (MD) simulations using explicit water as solvent and three different carbohydrate force fields, namely, GLYCAM06, PARM22/SU01, and CHARMM2011, were employed for the interpretation of experimental data. Overall, the force field based MD simulations are able to reproduce the experimental data and the ? torsion angle at the beta-(1?3)-linkage is concluded to be flexible. In addition, different minor states were present for the three force fields with either anti-? or non-exo-anomeric conformations. Transitions between the exo-anomeric and the non-exo-anomeric conformations for the f torsion angle at the beta-(1?4)-linkage in one of the MD simulations were analyzed in detail. It was found that hydrogen-bonding water molecules, interresidue hydrogen bonds and the transitions between antiperiplanar and synperiplanar conformations for the tH torsion angle of an N-acetyl group were all essential in the description of the glycosidic transition process. In particular, the transition of tH may be a general way of regulating other transitions into less populated but biologically important conformational regions.

  • 990.
    Zaccheus, Mona V.
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ali, Tara
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Cloeckaert, Axel
    Zygmunt, Michel S.
    Weintraub, Andrej
    Iriarte, Maite
    Moriyon, Ignacio
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    The Epitopic and Structural Characterization of Brucella suis Biovar 2 O-Polysaccharide Demonstrates the Existence of a New M-Negative C-Negative Smooth Brucella Serovar2013In: PLoS ONE, ISSN 1932-6203, E-ISSN 1932-6203, Vol. 8, no 1, p. e53941-Article in journal (Refereed)
    Abstract [en]

    The brucellae are Gram-negative bacteria that cause an important zoonosis. Studies with the main Brucella species have shown that the O-antigens of the Brucella smooth lipopolysaccharide are alpha-(1 -> 2) and alpha-(1 -> 3)-linked N-formyl-perosamine polysaccharides that carry M, A and C (A = M, A>M and A<M) epitopes relevant in serodiagnosis and typing. We report that, in contrast to the B. suis biovar 1 O-antigen used as a reference or to all described Brucella O-antigens, B. suis biovar 2 O-antigen failed to bind monoclonal antibodies of C (A = M), C (M>A) and M specificities. However, the biovar 2 O-antigen bound monoclonal antibodies to the Brucella A epitope, and to the C/Y epitope shared by brucellae and Yersinia enterocolitica O:9, a bacterium that carries an N-formyl-perosamine O-antigen in exclusively alpha-(1 -> 2)-linkages. By C-13 NMR spectroscopy, B. suis biovar 1 but not B. suis biovar 2 or Y.enterocolitica O:9 polysaccharide showed the signal characteristic of alpha-(1 -> 3)-linked N-formyl-perosamine, indicating that biovar 2 may altogether lack this linkage. Taken together, the NMR spectroscopy and monoclonal antibody analyses strongly suggest a role for alpha-(1 -> 3)-linked N-formyl-perosamine in the C (A = M) and C (M>A) epitopes. Moreover, they indicate that B. suis biovar 2 O-antigen lacks some lipopolysaccharide epitopes previously thought to be present in all smooth brucellae, thus representing a new brucella serovar that is M-negative, C-negative. Serologically and structurally this new serovar is more similar to Y. enterocolitica O:9 than to other brucellae.

  • 991.
    Zaccheus, Mona V.
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Broeker, Nina K.
    Lundborg, Magnus
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Uetrecht, Charlotte
    Barbirz, Stefanie
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Structural studies of the O‐antigen polysaccharide from Escherichia coli TD2158 having O18 serogroup specificity and aspects of its interaction with the tailspike endoglycosidase of the infecting bacteriophage HK6202012In: Carbohydrate Research, ISSN 0008-6215, E-ISSN 1873-426X, Vol. 357, p. 118-125Article in journal (Refereed)
    Abstract [en]

    We have analyzed the O-antigen polysaccharide of the previously uncharacterized Escherichia coli strain TD2158 which is a host of bacteriophage HK620. This bacteriophage recognizes and cleaves the polysaccharide with its tailspike protein (TSP). The polysaccharide preparation as well as oligosaccharides obtained from HK620TSP endoglycosidase digests were analyzed with NMR spectroscopy. Additionally, sugar analysis was performed on the O-antigen polysaccharide and MALDI-TOF MS was used in oligosaccharide analysis. The present study revealed a heterogeneous polysaccharide with a hexasaccharide repeating unit of the following structure: α-D-Glcp-(1→6|) →2)-α-L-Rhap-91→6)-α-D-Glcp-(1→4)-α-D-Ga|lp-(1→3)-α-D-GlcpNAc-(1→ β-D-Glcp/β-D-GlcpNAc-(1→3) A repeating unit with a D-GlcNAc substitution of D-Gal has been described earlier as characteristic for serogroup O18A1. Accordingly, we termed repeating units with D-Glc substitution at D-Gal as O18A2. NMR analyses of the polysaccharide confirmed that O18A1- and O18A2-type repeats were present in a 1:1 ratio. However, HK620TSP preferentially bound the D-GlcNAc-substituted O18A1-type repeating units in its high affinity binding pocket with a dissociation constant of 140 μM and disfavored the O18A2-type having a β-D-Glcp-(1→3)-linked group. As a result, in hexasaccharide preparations, O18A1 and O18A2 repeats were present in a 9:1 ratio stressing the clear preference of O18A1-type repeats to be cleaved by HK620TSP.

  • 992.
    Zain, Rula
    Stockholm University, Faculty of Science.
    Nucleoside H-phosphonothioates: synthesis, oxidation and ³¹P NMR studies1995Doctoral thesis, comprehensive summary (Other academic)
  • 993.
    Zhao, Gui-Ling
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Catalytic asymmetric Baylis–Hillman reactions and surroundings2010In: Catalytic Asymmetric Conjugate Reactions / [ed] Armando Córdova, Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA , 2010, 1, p. 393-438Chapter in book (Other academic)
  • 994.
    Zhao, Gui-Ling
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Córdova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    ECAs of organolithium reagents, Grignard reagents, and examples of Cu-catalyzed ECAs2010In: Catalytic Asymmetric Conjugate Reactions / [ed] Armando Córdova, Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA , 2010, 1, p. 145-167Chapter in book (Other academic)
  • 995.
    Zhao, Gui-Ling
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dziedzic, Pawel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ullah, Farman
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Eriksson, Lars
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry, Department of Structural Chemistry.
    Córdova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Organocatalytic enantioselective domino synthesis of highly functionalized cyclohexanes with an all-carbon quaternary stereocenter2009In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 50, no 26, p. 3458-3462Article in journal (Refereed)
    Abstract [en]

    A highly enantioselective organocatalytic domino Michael/aldol reaction is presented. The reaction is catalyzed by chiral amines and gives access to highly functionalized cyclohexanes with one all-carbon quaternary stereocenter and multiple chiral stereocenters in high yields and 83–98% ee.

  • 996.
    Zhao, Gui-Ling
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Hafrén, Jonas
    Deiana, Luca
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Córdova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Heterogeneous "organoclick" derivatization of polysaccharides: Photochemical thiol-ene click modification of solid cellulose2010In: Macromolecular rapid communications, ISSN 1022-1336, E-ISSN 1521-3927, Vol. 31, no 8, p. 740-744Article in journal (Refereed)
    Abstract [en]

    A simple and direct method for derivatization of solid polysaccharides is presented. The novel methodology is based on the combination of organic acid-catalyzed esterification or etherification and photochemical thiol-ene click derivatization of a heterogeneous polysaccharide. The solid cellulose was “organoclick” modified with aryl, alkyl and polyester groups, respectively. The modification allows for a highly modular and metal free surface modification of solid polysaccharides.

  • 997.
    Zhao, Gui-Ling
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Lin, Shuangzheng
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Korotvicka, Ales
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Deiana, Luca
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kullberg, Martin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Córdova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Asymmetric synthesis of Maraviroc (UK-427,857)2010In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 352, no 13, p. 2291-2298Article in journal (Refereed)
    Abstract [en]

    The asymmetric synthesis of Maraviroc (UK-427,857), a chemochine receptor 5 (CCR-5) receptor antagonist, based on an expeditious organocatalytic enantioselective assembly of the chiral β-amino aldehyde key fragment is presented. The reactions were performed on a gram-scale and allow for the rapid construction of new Maraviroc analogues.

  • 998.
    Zhao, Gui-Ling
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ullah, Farman
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Luca, Deiana
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Lin, Shuangzheng
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Zhang, Qiong
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry, Structural Chemistry.
    Ibrahem, Ismail
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dziedzic, Pawel
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Córdova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dynamic kinetic asymmetric transformation (DYKAT) by combined amine- and transition-metal-catalyzed enantioselective cycloisomerization2010In: Chemistry: a European Journal, ISSN 0947-6539, Vol. 16, no 5, p. 1585-1591Article in journal (Refereed)
  • 999.
    Zhao, Tony
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds2015Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis is focused on the development of new palladium and copper- mediated reactions for functionalization of alkenes and propargylic alcohol derivatives. The synthetic utility of the 1,2-diborylated butadienes synthesized in one of these processes has also been demonstrated.

    We have developed an efficient procedure for the synthesis of allenyl boronates from propargylic carbonates and acetates. This was achieved by using a bimetallic system of palladium and copper or silver as co-catalyst. The reactions were performed under mild conditions for the synthesis of a variety of allenyl boronates. Furthermore, the synthesis of 1,2-diborylated butadienes was achieved with high diastereoselectivity from propargylic epoxides. The reactivity of the 1,2-diborylated butadienes with aldehydes was studied. It was found that the initial allylboration reaction proceeds via an allenylboronate intermediate. The allenylboronate reacts readily with an additional aldehyde to construct 2-ethynylbutane-1,4-diols with moderate to high diastereoselectivity.

    We have also studied the copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates. It was also shown that a transfer of chirality occurred when an enantioenriched starting material was used.

    In the last part of the thesis, we have described a method for palladium-catalyzed functionalization of allylic C-H bonds for the selective synthesis of allylic silanes. The protocol only works under highly oxidative conditions which suggest a mechanism involving high oxidation state palladium intermediates.

  • 1000.
    Zhao, Tony S. N.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Copper and Palladium-Mediated Transformationsof Allylic and Propargylic Substrates2014Licentiate thesis, monograph (Other academic)
    Abstract [en]

    This thesis is focused on the development of new palladium and copper-mediated reactions for functionalization of alkenes and propargylic alcohol derivatives. We have developed an efficient procedure for the synthesis of allenyl and propargyl boronate from propargylic carbonates and acetates. The reactions were performed under mild conditions for the synthesis of a variety of allenyl boronates. We have also observed a switch of regioselectivity for the formation of propargylic boronates using CuCl as a co-catalyst. This is, as far as we know, the first metal-catalyzed reaction for the synthesis of propargylic boronates. Furthermore, the synthesis of 1,2-diborylated butadienes was achieved with high diastereoselectivity from propargylic epoxides. A wide variety of propargylic epoxides could be converted to the corresponding dienes and this is the first catalytic protocol to form 1,2-diborylated butadienes.

    We have also studied the copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates. Depending on the temperature, two different regioselective outcomes were observed. It was also shown that a transfer of chirality occurred when an enantioenriched starting material was used.

    In the last part of the thesis, we have described a method for palladium-catalyzed functionalization of allylic C-H bonds for selective synthesis of allylic silanes. The reaction is regioselective and gives only the linear allylic silane. The protocol only works under highly oxidative conditions which suggest a mechanism involving high oxidation state palladium intermediates.

1718192021 951 - 1000 of 1017
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