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  • 1.
    Akkarasamiyo, Sunisa
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sawadjoon, Supaporn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Orthaber, Andreas
    Samec, Joseph S. M.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Tsuji-Trost Reaction of Non-Derivatized Allylic Alcohols2018In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 14, p. 3488-3498Article in journal (Refereed)
    Abstract [en]

    Palladium-catalyzed allylic substitution of non-derivatized enantioenriched allylic alcohols with a variety of uncharged N-, S-, C- and O-centered nucleophiles using a bidentate BiPhePhos ligand is described. A remarkable effect of the counter ion (X) of the XPd[kappa(2)-BiPhePhos][kappa(3)-C3H5] was observed. When ClPd[kappa(2)-BiPhePhos][eta(3)-C3H5] (complexI) was used as catalyst, non-reproducible results were obtained. Study of the complex by X-ray crystallography, (PNMR)-P-31 spectroscopy, and ESI-MS showed that a decomposition occurred where one of the phosphite ligands was oxidized to the corresponding phosphate, generating ClPd[kappa(1)-BiPhePhosphite-phosphate][eta(3)-C3H5] species (complexII). When the chloride was exchanged to the weaker coordinating OTf- counter ion the more stable Pd[kappa(2)-BiPhePhos][eta(3)-C3H5](+)+[OTf] (-) (complexIII) was formed. ComplexIII performed better and gave higher enantiospecificities in the substitution reactions. ComplexIII was evaluated in Tsuji-Trost reactions of stereogenic non-derivatized allylic alcohols. The desired products were obtained in good to excellent yields (71-98%) and enantiospecificities (73-99%) for both inter- and intramolecular substitution reactions with only water generated as a by-product. The methodology was applied to key steps in total synthesis of (S)-cuspareine and (+)-lentiginosine. A reaction mechanism involving a palladium hydride as a key intermediate in the activation of the hydroxyl group is proposed in the overall transformation.

  • 2.
    Bartholomeyzik, Teresa
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pendrill, Robert
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Lihammar, Richard
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Jiang, Tuo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kinetics and Mechanism of the Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes2018In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 1, p. 298-309Article in journal (Refereed)
    Abstract [en]

    Pd-catalyzed C-C bond-forming reactions under oxidative conditions constitute a class of important and widely used synthetic protocols. This Article describes a mechanistic investigation of the arylating carbocyclization of allenynes using boronic acids and focuses on the correlation between reaction conditions and product selectivity. Isotope effects confirm that either allenic or propargylic C-H activation occurs directly after substrate binding. With an excess of H2O, a triene product is selectively formed via allenic C-H activation. The latter C-H activation was found to be turnover-limiting and the reaction zeroth order in reactants as well as the oxidant. A dominant feature is continuous catalyst activation, which was shown to occur even in the absence of substrate. Smaller amounts of H2O lead to mixtures of triene and vinylallene products, where the latter is formed via propargylic C-H activation. The formation of triene occurs only in the presence of ArB(OH)(2). Vinylallene, on the other hand, was shown to be formed by consumption of (ArBO)(3) as a first-order reactant. Conditions with sub-stoichiometric BF3 center dot OEt2 gave selectively the vinylallene product, and the reaction is first order in PhB(OH)(2). Both C-H activation and transmetalation influence the reaction rate. However, with electron-deficient ArB(OH)(2), C-H activation is turnover-limiting. It was difficult to establish the order of transmetalation vs C-H activation with certainty, but the results suggest that BF3 center dot OEt2 promotes an early transmetalation. The catalytically active species were found to be dependent on the reaction conditions, and H2O is a crucial parameter in the control of selectivity.

  • 3. Betterley, Nolan M.
    et al.
    Kerdphon, Sutthichat
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Chaturonrutsamee, Suppisak
    Kongsriprapan, Sopanat
    Surawatanawong, Panida
    Soorukram, Darunee
    Pohmakotr, Manat
    Andersson, Pher G.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Reutrakul, Vichai
    Kuhakarn, Chutima
    Bi(OTf)(3) Enabled C-F Bond Cleavage in HFIP: Electrophilic Aromatic Formylation with Difluoro(phenylsulfanyl)methane2018In: Asian Journal of Organic Chemistry, ISSN 2193-5807, Vol. 7, no 8, p. 1642-1647Article in journal (Refereed)
    Abstract [en]

    Bismuth(III) trifluoromethanesulfonate [Bi(OTf)(3)] mediated mild electrophilic aromatic formylation utilizing difluoro(phenylsulfanyl)methane (PhSCF2H) as a formylating agent in hexafluoro-2-propanol (HFIP) as a recyclable ionizing solvent has been developed. The active formylating species was generated via C-F bond cleavage and was characterized to be a bis(phenylsulfanyl)methyl cation by experimental and computational H-1 and C-13 NMR.

  • 4.
    Blomberg, Margareta R. A.
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ädelroth, Pia
    Stockholm University, Faculty of Science, Department of Biochemistry and Biophysics.
    Mechanisms for enzymatic reduction of nitric oxide to nitrous oxide - A comparison between nitric oxide reductase and cytochrome c oxidase2018In: Biochimica et Biophysica Acta - Bioenergetics, ISSN 0005-2728, E-ISSN 1879-2650, Vol. 1859, no 11, p. 1223-1234Article in journal (Refereed)
    Abstract [en]

    Cytochrome c oxidases (CcO) reduce O-2 to H2O in the respiratory chain of mitochondria and many aerobic bacteria. In addition, some species of CcO can also reduce NO to N2O and water while others cannot. Here, the mechanism for NO-reduction in CcO is investigated using quantum mechanical calculations. Comparison is made to the corresponding reaction in a true cytochrome c-dependent NO reductase (cNOR). The calculations show that in cNOR, where the reduction potentials are low, the toxic NO molecules are rapidly reduced, while the higher reduction potentials in CcO lead to a slower or even impossible reaction, consistent with experimental observations. In both enzymes the reaction is initiated by addition of two NO molecules to the reduced active site, forming a hyponitrite intermediate. In cNOR, N2O can then be formed using only the active-site electrons. In contrast, in CcO, one proton-coupled reduction step most likely has to occur before N2O can be formed, and furthermore, proton transfer is most likely rate-limiting. This can explain why different CcO species with the same heme alpha(3)-Cu active site differ with respect to NO reduction efficiency, since they have a varying number and/or properties of proton channels. Finally, the calculations also indicate that a conserved active site valine plays a role in reducing the rate of NO reduction in CcO.

  • 5.
    Brea, Oriana
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Luna, Alberto
    Diaz, Cristina
    Corral, Ines
    Molecular Modelling of the H-2-Adsorptive Properties of Tetrazolate-Based Metal-Organic Frameworks: From the Cluster Approach to Periodic Simulations2018In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 19, no 11, p. 1349-1357Article in journal (Refereed)
    Abstract [en]

    Hydrogen has been proposed as a long-term non-fossil fuel to be used in a future ideal carbon-neutral energetic economy. However, its low volumetric energy density hinders its storage and transportation. Metal-organic frameworks (MOFs) represent very promising materials for this purpose due to their very extended surface areas. Azolates, in particular tetrazolates, are - together with carboxylate functionalities - very common organic linkers connecting metallic secondary building units in MOFs. This study addresses, from a theoretical perspective, the H-2 adsorptive properties of tetrazolate linkers at the molecular level, following a size-progressive approach. Specifically, we have investigated how the physisorption energies and geometries are affected when changing the environment of the linker by considering the azolates in the gas phase, immersed in a finite cluster, or being part of an infinite extended crystal material. Furthermore, we also study the H-2 adsorptive capacity of these linkers within the cluster model.

  • 6.
    Brea, Oriana
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mó, Otilia
    Yáñez, Manuel
    Merced Montero-Campillo, M.
    Alkorta, Ibon
    Elguero, José
    Are beryllium-containing biphenyl derivatives efficient anion sponges?2018In: Journal of Molecular Modeling, ISSN 1610-2940, E-ISSN 0948-5023, Vol. 24, no 1, article id 16Article in journal (Refereed)
    Abstract [en]

    The structures and stabilities of 2,2'-diBeX-1,1'-biphenyl (X = H, F, Cl, CN) derivatives and their affinities for F-, Cl-, and CN- were theoretically investigated using a B3LYP/6-311 + G(3df, 2p)//B3LYP/6-31 + G(d,p) model. The results obtained show that the 2,2'-diBeX-1,1'-biphenyl derivatives (X = H, F, Cl, CN) exhibit very high F-, Cl-, and CN- affinities, albeit lower than those reported before for their 1,8-diBeX-naphthalene analogs, in spite of the fact that the biphenyl derivatives are more flexible than their naphthalene counterparts. Nevertheless, some of the biphenyl derivatives investigated are predicted to have anion affinities larger than those measured for SbF5, which is considered one of the strongest anion capturers. Therefore, although weaker than their naphthalene analogs, the 2,2'-diBeX-1,1'-biphenyl derivatives can still be considered powerful anion sponges. This study supports the idea that compounds containing -BeX groups in chelating positions behave as anion sponges due to the electron-deficient nature and consequently high intrinsic Lewis acidity of these groups.

  • 7.
    Colas, Kilian
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mendoza, Abraham
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Iterative Synthesis of Pluripotent Thioethers through Controlled Redox Fluctuation of Sulfur2018In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, Vol. 29, no 10, p. 1329-1333Article in journal (Refereed)
    Abstract [en]

    Target- and diversity-oriented syntheses are based on diverse building blocks, whose preparation requires discrete design and constructive alignment of different chemistries. To enable future automation of the synthesis of small molecules, we have devised a unified strategy that serves the divergent synthesis of unrelated scaffolds such as carbonyls, olefins, organometallics, halides, and boronic esters. It is based on iterations of a nonelectrophilic Pummerer-type C-C coupling enabled by turbo -organomagnesium amides that we have recently reported. The pluripotency of sulfur allows the central building blocks to be obtained by regulating C-C bond formation through control of its redox state.

  • 8.
    Cortés González, Miguel A.
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Nordeman, Patrik
    Bermejo Gómez, Antonio
    Stockholm University, Faculty of Science, Department of Organic Chemistry. AstraZeneca PET Centre at Karolinska Institutet, Sweden.
    Meyer, Denise N.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Antoni, Gunnar
    Schou, Magnus
    Szabó, Kálmán J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    [F-18]fluoro-benziodoxole: a no-carrier-added electrophilic fluorinating reagent. Rapid, simple radiosynthesis, purification and application for fluorine-18 labelling2018In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 54, no 34, p. 4286-4289Article in journal (Refereed)
    Abstract [en]

    Operationally simple radiosynthesis and purification of [F-18]fluoro-benziodoxole was developed starting from a cyclotron produced [F-18]F- precursor, [F-18]TBAF, and tosyl-benziodoxole. The synthetic utility of [F-18]fluoro-benziodoxole was demonstrated by electrophilic fluorocyclization of o-styrilamides proceeding with high RCC (typically 50-90%) and high molar activity (up to 396 GBq mol(-1)).

  • 9. Daikoku, S.
    et al.
    Pendrill, Robert
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kanie, Y.
    Ito, Y.
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kanie, O.
    Synthesis and structural investigation of a series of mannose-containing oligosaccharides using mass spectrometry2018In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 16, no 2, p. 228-238Article in journal (Refereed)
    Abstract [en]

    A series of compounds associated with naturally occurring and biologically relevant glycans consisting of alpha-mannosides were prepared and analyzed using collision-induced dissociation (CID), energy-resolved mass spectrometry (ERMS), and H-1 nuclear magnetic resonance spectroscopy. The CID experiments of sodiated species of disaccharides and ERMS experiments revealed that the order of stability of mannosyl linkages was as follows: 6-linked > 4-linked >= 2-linked > 3-linked mannosyl residues. Analysis of linear trisaccharides revealed that the order observed in disaccharides could be applied to higher glycans. A branched trisaccharide showed a distinct dissociation pattern with two constituting disaccharide ions. The estimation of the content of this ion mixture was possible using the disaccharide spectra. The hydrolysis of mannose linkages at 3- and 6-positions in the branched trisaccharide revealed that the 3-linkage was cleaved twice as fast as the 6-linkage. It was observed that the solution-phase hydrolysis and gas-phase dissociation have similar energetics.

  • 10. Das, Biswanath
    et al.
    Daver, Henrik
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pyrkosz-Bulska, Monika
    Gumienna-Kontecka, Elzbieta
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Nordlander, Ebbe
    An Unsymmetric Ligand with a N5O2 Donor Set and Its Corresponding Dizinc Complex: A Structural and Functional Phosphoesterase Model2018In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 36, p. 4004-4013Article in journal (Refereed)
    Abstract [en]

    To mimic the active sites of the hydrolytic enzyme zinc phosphotriesterase, a new dinucleating unsymmetric ligand, PICIMP (2-{[2-hydroxy-5-methyl-3-({[(1-methyl-1H-imidazol-2-yl)methyl](pyridin-2-ylmethyl)amino}methyl)benzyl][(1-methyl-1H-imidazol-2-yl)methyl]amino}acetic acid), has been synthesized and characterized. The hydrolytic efficacy of the complex solution (PICIMP/ZnCl2 = 1:2) has been investigated using bis-(2,4-dinitrophenyl)phosphate (BDNPP), a DNA analogue substrate. Speciation studies were undertaken by potentiometric titrations at varying pH for both the ligand and the corresponding dizinc complex to elucidate the formation of the active hydrolysis catalyst; these studies reveal that the dinuclear zinc(II) complexes, [Zn-2(PICIMP)](2+) and [Zn-2(PICIMP)(OH)](+) predominate in solution above pH 4. The obtained pK(a) of 7.44 for the deprotonation of water suggests formation of a bridging hydroxide between the two Zn-II ions. Kinetic investigations of BDNPP hydrolysis over the pH range 5.5-10.5 have been performed. The cumulative results indicate the hydroxo-bridged dinuclear Zn-II complex [Zn-2(PICIMP)(mu-OH)](+) as the effective catalyst. Density functional theory calculations were performed to investigate the detailed reaction mechanism. The calculations suggest that the bridging hydroxide becomes terminally coordinated to one of the zinc ions before performing the nucleophilic attack in the reaction.

  • 11.
    Daver, Henrik
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Algarra, Andrés G.
    Rebek, Julius
    Harvey, Jeremy N.
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mixed Explicit-Implicit Solvation Approach for Modeling of Alkane Complexation in Water-Soluble Self-Assembled Capsules2018In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 39, p. 12527-12537Article in journal (Refereed)
    Abstract [en]

    The host-guest binding properties of a water-soluble resorcinarene-based cavitand are examined using density functional theory methodology. Experimentally, the cavitand has been observed to self-assemble in aqueous solution into both 1:1 and 2:1 host/guest complexes with hydrophobic guests such as n-alkanes. For n-decane, equilibrium was observed between the 1:1 and 2:1 complexes, while 1:1 complexes are formed with shorter n-alkanes and 2:1 complexes are formed with longer ones. These findings are used to assess the standard quantum chemical methodology. It is first shown that a rather advanced com- putational protocol (B3LYP-D3(BJ)/6-311+G(2d,2p) with COSMO-RS and quasi-rigid-rotor-harmonic-oscillator) gives very large errors. Systematic examination of the various elements of the methodology shows that the error stems from the implicit solvation model. A mixed explicit-implicit solvation protocol is developed that involves a parametrization of the hydration free energy of water such that water cluster formation in water is predicted to be thermoneutral. This new approach is demonstrated to lead to a major improvement in the calculated binding free energies of n-alkanes, reproducing very well the 1:1 versus 2:1 host/guest binding trends.

  • 12.
    Di Francesco, Davide
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Subbotina, Elena
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Rautiainen, Sari
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Samec, Joseph S. M.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ductile Pd-Catalysed Hydrodearomatization of Phenol-Containing Bio-Oils Into Either Ketones or Alcohols using PMHS and H2O as Hydrogen Source2018In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 360, no 20, p. 3924-3929Article in journal (Refereed)
    Abstract [en]

    A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water concentrations. As phenolic bio-oil examples cardanol and beech wood tar creosote were studied as substrate to the developed reaction conditions. Cardanol was hydrodearomatized into 3-pentadecylcyclohexanone in excellent yield. From beech wood tar creosote, a mixture of cyclohexanols was produced. No hydrodeoxygenation occurred, suggesting the applicability of the reported method for the production of ketone-alcohol oil from biomass.

  • 13. Dorau, Robin
    et al.
    Görbe, Tamás
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Svedendahl Humble, Maria
    Improved Enantioselectivity of Subtilisin Carlsberg Towards Secondary Alcohols by Protein Engineering2018In: ChemBioChem (Print), ISSN 1439-4227, E-ISSN 1439-7633, Vol. 19, no 4, p. 338-346Article in journal (Refereed)
    Abstract [en]

    Generally, the catalytic activity of subtilisin Carlsberg (SC) for transacylation reactions with secondary alcohols in organic solvent is low. Enzyme immobilization and protein engineering was performed to improve the enantioselectivity of SC towards secondary alcohols. Possible amino-acid residues for mutagenesis were found by combining available literature data with molecular modeling. SC variants were created by site-directed mutagenesis and were evaluated for a model transacylation reaction containing 1-phenylethanol in THF. Variants showing high E values (>100) were found. However, the conversions were still low. A second mutation was made, and both the E values and conversions were increased. Relative to that shown by the wild type, the most successful variant, G165L/M221F, showed increased conversion (up to 36 %), enantioselectivity (E values up to 400), substrate scope, and stability in THF.

  • 14.
    Erbing, Elis
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sanz-Marco, Amparo
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Vazquez-Romero, Ana
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Malmberg, Jesper
    Johansson, Magnus J.
    Gomez-Bengoa, Enrique
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Base- and Additive-Free Ir-Catalyzed ortho-Iodination of Benzoic Acids: Scope and Mechanistic Investigations2018In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 8, no 2, p. 920-925Article in journal (Refereed)
    Abstract [en]

    A protocol for the C-H activation/iodination of benzoic acids catalyzed by a simple iridium complex has been developed. The method described in this paper allows the ortho-selective iodination of a variety of benzoic acids under extraordinarily mild conditions in the absence of any additive or base in 1,1,1,3,3,3-hexafluoroisopropanol as the solvent. The iridium catalyst used tolerates air and moisture, and selectively gives ortho-iodobenzoic acids with high conversions. Mechanistic investigations revealed that an Ir(III)/Ir(V) catalytic cycle operates, and that the unique properties of HFIP enables the C-H iodination using the carboxylic moiety as a directing group.

  • 15.
    González Miera, Greco
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martínez-Castro, Elisa
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Martín-Matute, Belén
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Acceptorless Alcohol Dehydrogenation: OH vs NH Effect in Bifunctional NHC–Ir(III) Complexes2018In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 37, no 5, p. 636-644Article in journal (Refereed)
    Abstract [en]

    Bifunctional complexes bearing N-heterocyclic carbene (NHC) ligands functionalized with hydroxy or amine groups were synthesized to measure the beneficial effect of different modes of metal–ligand cooperation in the acceptorless dehydrogenation of alcohols. In comparison to complexes with an amine moiety, hydroxy-functionalized iridium catalysts showed superior activity. In contrast to alcohols, 1,4-diols underwent cyclization to give the corresponding tetrahydrofurans without involving dehydrogenation processes. Mechanistic investigations to rationalize the “OH effect” in these types of complexes have been undertaken.

  • 16.
    Gudmundsson, Arnar
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Gustafson, Karl P. J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Yang, Bin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Efficient Formation of 2,3-Dihydrofurans via Iron-Catalyzed Cycloisomerization of alpha-Allenols2018In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 8, no 1, p. 12-16Article in journal (Refereed)
    Abstract [en]

    Herein, we report a highly efficient iron-catalyzed intramolecular nucleophilic cyclization of alpha-allenols to furnish substituted 2,3-dihydrofurans under mild reaction conditions. A highly diastereoselective variant of the reaction was developed as well, giving diastereomeric ratios of up to 98:2. The combination of the iron-catalyzed cycloisomerization with enzymatic resolution afforded the 2,3-dihydrofuran in high ee. A detailed DFT study provides insight into the reaction mechanism and gives a rationalization for the high chemo-and diastereoselectivity.

  • 17. Gustafsson, Nina M. S.
    et al.
    Färnegårdh, Katarina
    Stockholm University, Faculty of Science, Department of Organic Chemistry. Stockholm University, Science for Life Laboratory (SciLifeLab). Kancera AB, Sweden.
    Bonagas, Nadilly
    Ninou, Anna Huguet
    Groth, Petra
    Wiita, Elisee
    Jönsson, Mattias
    Hallberg, Kenth
    Lehto, Jemina
    Pennisi, Rosa
    Martinsson, Jessica
    Norström, Carina
    Hollers, Jessica
    Schultz, Johan
    Andersson, Martin
    Markova, Natalia
    Marttila, Petra
    Kim, Baek
    Norin, Martin
    Olin, Thomas
    Helleday, Thomas
    Targeting PFKFB3 radiosensitizes cancer cells and suppresses homologous recombination2018In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 9, article id 3872Article in journal (Refereed)
    Abstract [en]

    The glycolytic PFKFB3 enzyme is widely overexpressed in cancer cells and an emerging anticancer target. Here, we identify PFKFB3 as a critical factor in homologous recombination (HR) repair of DNA double-strand breaks. PFKFB3 rapidly relocates into ionizing radiation (IR)-induced nuclear foci in an MRN-ATM-gamma H2AX-MDC1-dependent manner and co-localizes with DNA damage and HR repair proteins. PFKFB3 relocalization is critical for recruitment of HR proteins, HR activity, and cell survival upon IR. We develop KAN0438757, a small molecule inhibitor that potently targets PFKFB3. Pharmacological PFKFB3 inhibition impairs recruitment of ribonucleotide reductase M2 and deoxynucleotide incorporation upon DNA repair, and reduces dNTP levels. Importantly, KAN0438757 induces radiosensitization in transformed cells while leaving non-transformed cells unaffected. In summary, we identify a key role for PFKFB3 enzymatic activity in HR repair and present KAN0438757, a selective PFKFB3 inhibitor that could potentially be used as a strategy for the treatment of cancer.

  • 18.
    Görbe, Tamás
    et al.
    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.
    Heterogeneous Acid-Catalyzed Racemization of Tertiary Alcohols2018In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 1, p. 77-80Article in journal (Refereed)
    Abstract [en]

    Tertiary alcohols are important structural motifs in natural products and building blocks in organic synthesis but only few methods are known for their enantioselective preparation. Chiral resolution is one of these approaches that leaves one enantiomer (50% of the material) unaffected. An attractive method to increase the efficiency of those resolutions is to racemize the unaffected enantiomer. In the present work, we have developed a practical racemization protocol for tertiary alcohols. Five different acidic resin materials were tested. The Dowex 50WX8 was the resin of choice since it was capable of racemizing tertiary alcohols without any byproduct formation. Suitable solvents and a biphasic system were investigated, and the optimized system was capable of racemizing differently substituted tertiary alcohols.

  • 19.
    Hamark, Christoffer
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Pendrill, Robert
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Landström, Jens
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dotson Fagerström, Alexandra
    Sandgren, Mats
    Ståhlberg, Jerry
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Enantioselective Binding of Propranolol and Analogues Thereof to Cellobiohydrolase Cel7A2018In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 68, p. 17975-17985Article in journal (Refereed)
    Abstract [en]

    At the catalytic site for the hydrolysis of cellulose the enzyme cellobiohydrolase Cel7A binds the enantiomers of the adrenergic beta-blocker propranolol with different selectivity. Methyl-to-hydroxymethyl group modifications of propranolol, which result in higher affinity and improved selectivity, were herein studied by H-1,H-1 and H-1,C-13 scalar spin-spin coupling constants as well as utilizing the nuclear Overhauser effect (NOE) in conjunction with molecular dynamics simulations of the ligands per se, which showed the presence of all-antiperiplanar conformations, except for the one containing a vicinal oxygen-oxygen arrangement governed by the gauche effect. For the ligand-protein complexes investigated by NMR spectroscopy using, inter alia, transferred NOESY and saturation-transfer difference (STD) NMR experiments the S-isomers were shown to bind with a higher affinity and a conformation similar to that preferred in solution, in contrast to the R-isomer. The fact that the S-form of the propranolol enantiomer is pre-arranged for binding to the protein is also observed for a crystal structure of dihydroxy-(S)-propranolol and Cel7A presented herein. Whereas the binding of propranolol is entropy driven, the complexation with the dihydroxy analogue is anticipated to be favored also by an enthalpic term, such as for its enantiomer, that is, dihydroxy-(R)-propranolol, because hydrogen-bond donation replaces the corresponding bonding from hydroxyl groups in glucosyl residues of the natural substrate. In addition to a favorable entropy component, albeit lesser in magnitude, this represents an effect of enthalpy-to-entropy compensation in ligand-protein interactions.

  • 20.
    Heshmat, Mojgan
    Stockholm University, Faculty of Science, Department of Organic Chemistry. Vrije Universiteit Amsterdam, The Netherlands.
    Unraveling the Origin of Solvent Induced Enantioselectivity in the Henry Reaction with Cinchona Thiourea as Catalyst2018In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 40, p. 7974-7982Article in journal (Refereed)
    Abstract [en]

    In this work, we report an energy decomposition and electronic structure analysis using DFT calculations for the C-C coupling step in the Henry reaction with cinchona thiourea as catalyst and DMF solvent to unravel the origin of enantioselectivity. We found that the conformation of flexible thiourea moiety is affected by the solvent, and in the preferred conformation of thiourea in strong Lewis basic DMF solvent, the N-H sites are in the opposite direction, i.e., in trans conformation. Hence, the thiourea moiety acts via single hydrogen bonding with substrates. The conformation of the substrates with respect to the forming C-C bond plays critical role to increase orbital interaction between two substrates and enhances hydrogen bond strength between substrates and catalyst, which in turn stabilizes the positive charge developing on the catalyst at the transition state for one of the enantiomers (S). Thus, the enantioselectivity has electronic structure origin. The stronger H-bond formation in the S enantiomer has been confirmed by the calculated IR spectra and is in agreement with thus far experimental and computational results.

  • 21.
    Heshmat, Mojgan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Privalov, Timofei
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    H-2 Cleavage by Frustrated Lewis Pairs Characterized by the Energy Decomposition Analysis of Transition States: An Alternative to the Electron Transfer and Electric Field Models2018In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 36, p. 7202-7211Article in journal (Refereed)
    Abstract [en]

    Knowing that the Papai's electron transfer (ET) and the Grimme's electric field (EF) models draw attention to somewhat different physical aspects, we are going to systematically (re)examine interactions in the transition states (TSs) of the heterolytic H-2-cleavage by the Frustrated Lewis Pairs (FLPs). Our main vehicle is the quantitative energy decomposition analysis (EDA), a powerful method for elucidation of interactions, plus the analysis of molecular orbitals (MOs). Herein, the Lewis acid (LA) is B(C6F5)(3) and the Lewis bases (LBs) are tBu(3)P, (o-C6H4Me)(3)P, 2,6-lutidine, 2,4,6-lutidine, MeN=C(Ph)Me imine, MeN(H)-C(H)PhMe amine, THF, 1,4-dioxane, and acetone. For a series of the phosphorus-, nitrogen-, and oxygen-bearing LBs plus B(C6F5)(3), we will show that (i) neither the electrostatic nor the orbital interactions dominate but instead both are essential alongside the Pauli repulsion and (ii) the frontier molecular orbitals (FMOs) of a TS can arise not only from the push-pull molecular orbital scheme by Papai et al., which directly involves the occupied sigma and the empty sigma* MOs of H-2, but also from a more intricate but energetically more fitting orbital interactions which have escaped notice thus far.

  • 22.
    Heshmat, Mojgan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Privalov, Timofei
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Structurally Flexible Oxocarbenium/Borohydride Ion Pair: Dynamics of Hydride Transfer on the Background of Conformational Roaming2018In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 23, p. 5098-5106Article in journal (Refereed)
    Abstract [en]

    We apply Born-Oppenheimer molecular dynamics to the practically significant [dioxane-H(+)-acetone]-[(C6F5)(3)B-H(-)] and [Et2O-H(+)-OCPr2][(C6F5)(3)B-H(-)] ion pair intermediates. Dynamics of hydride transfer in cation/anion ion pair takes place on the background of large amplitude configurational changes. Geometry of oxocarbenium/borohydride ion pairs is flexible, meaning that we uncover significant actual structural disorder at a finite temperature. Therefore, although the starting structure can be fairly close to the configurational area of the hydride transfer transition state (TS) and despite a low potential energy barrier (ca. 1.5 kcal/mol, according to the literature), already at T approximate to 325 K the system can remain ignorant of the TS region and move round and about (roam) in the configurational space for a period of time in the range between 10 and 100 ps. This indicates structural flexibility of oxocarbenium/borohydride ion pair on apparently a flat potential energy landscape of cation/anion interaction, and this has not been taken into consideration by the free energy estimations in static considerations made thus far. The difference between the dynamics-based representation of the system versus the static representation amounts to the difference between quasi-bimolecular versus unimolecular descriptions of the hydride transfer step.

  • 23.
    Heshmat, Mojgan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Privalov, Timofei
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Surprisingly Flexible Oxonium/Borohydride Ion Pair Configurations2018In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 15, p. 3713-3727Article in journal (Refereed)
    Abstract [en]

    We investigate the geometry of oxonium/borohydride ion pairs [ether-H(+) ether] [LA-H(-)] with dioxane, THF, and Et2O as ethers and B(C6F5)(3) as the Lewis acid (LA). The question is about possible location of the disolvated proton [ether -H(+) -ether], with respect to the hydride of the structurally complex [LA -H(-)] anion. Using Born Oppenheimer molecular dynamics and a comparison of the potential and free energies of the optimized configurations, we show that herein considered ion pairs are much more flexible geometrically than previously thought. Conformers with different locations of cations with respect to anions are governed by a flat energy -landscape. We found a novel configuration in which oxonium is below [LA-11((-))], with respect to the direction of borane -> hydride vector, and the proton -hydride distance is ca. 6 A. With calculations of the vibrational spectra of [ether-H(+)-ether][(C6F5)(3)B-H(-)] for dioxane, THF, and Et2O as ethers, we investigate the manifestation of SSLB-type (short, strong, low -barrier) hydrogen bonding in the OHO motif of an oxonium cation.

  • 24.
    Heshmat, Mojgan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Privalov, Timofei
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Water and a Borohydride/Hydronium Intermediate in the Borane-Catalyzed Hydrogenation of Carbonyl Compounds with H-2 in Wet Ether: A Computational Study2018In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 122, no 38, p. 8952-8962Article in journal (Refereed)
    Abstract [en]

    We have computationally evaluated water as an active Lewis base (LB) and introduced the borohydride/hydronium intermediate in the mechanism of B(C6F5)(3)-catalyzed hydrogenation of carbonyl compounds with H-2 in wet/moist ether. Our calculations extend the known frustrated Lewis pair mechanism of this reaction toward the inclusion of water as the active participant in all steps. Although the definition of the zero-energy point interweaves in comparison of the scenarios with and without water, we will be able to show that (i) water (hydrogen bonded to its molecular environment) can, in principle, act as a reasonably viable LB in cooperation with the borane Lewis acid such as B(C6F5)(3) but relatively a strong borane-water complexation can be the hindering factor; (ii) the herein-proposed borohydride/hydronium intermediates with the hydronium cation having three OH center dot center dot center dot ether hydrogen bonds or a combination of the OH center dot center dot center dot ether/OH center dot center dot center dot ketone hydrogen bonds appear to be as valid as the previously considered borohydride/oxonium or borohydride/oxocarbenium intermediates; (iii) the proton-coupled hydride transfer from the borohydride/hydronium to a ketone (acetone) has a reasonably low barrier. Our findings could be useful for better mechanistic understanding and further development of the aforementioned reaction.

  • 25. Ibrahem, Ismail
    et al.
    Iqbal, Muhammad Naeem
    Stockholm University, Faculty of Science, Department of Organic Chemistry. Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Verho, Oscar
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Eivazihollagh, Alireza
    Olsén, Peter
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Edlund, Håkan
    Tai, Cheuk-Wai
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Norgren, Magnus
    Johnston, Eric V.
    Copper Nanoparticles on Controlled Pore Glass and TEMPO for the Aerobic Oxidation of Alcohols2018In: ChemNanoMat, ISSN 2199-692X, Vol. 4, no 1, p. 71-75Article in journal (Refereed)
    Abstract [en]

    Herein, we report on the facile synthesis of a heterogeneous copper nanocatalyst and its combination with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) for the aerobic oxidation of alcohols to their corresponding carbonyl compounds. This low cost copper nanocatalyst was found to exhibit excellent recyclability, making it a highly attractive catalytic system from an economical and environmental point of view. Extensive characterization of the catalyst by a number of techniques revealed that it was comprised of well-dispersed Cu(I/II) nanoparticles with an average size of around 6nm.

  • 26.
    Jiang, Yan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Deiana, Luca
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Alimohammadzadeh, Rana
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Liu, Leifeng
    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).
    Cordova, Armando
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Highly Diastereo- and Enantioselective Cascade Synthesis of Bicyclic Lactams in One-Pot2018In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 9, p. 1158-1164Article in journal (Refereed)
    Abstract [en]

    A versatile and highly stereoselective synthetic route to functionalized bi- and tricyclic lactams (up to > 20:1 dr and 99% ee) in one pot from simple starting materials (allylic alcohols, enals, diamines and amino alcohols) using cascade transformations promoted by chiral amine/BrOnsted or metal/chiral amine/BrOnsted relay catalysis is disclosed. Here molecular oxygen is employed as the terminal oxidant for the latter relay catalysis approach.

  • 27. Jo, Sunhwan
    et al.
    Myatt, Daniel
    Qi, Yifei
    Doutch, James
    Clifton, Luke A.
    Im, Wonpil
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Multiple Conformational States Contribute to the 3D Structure of a Glucan Decasaccharide: A Combined SAXS and MD Simulation Study2018In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 122, no 3, p. 1169-1175Article in journal (Refereed)
    Abstract [en]

    The inherent flexibility of carbohydrates is dependent on stereochemical arrangements, and characterization of their influence and importance will give insight into the three-dimensional structure and dynamics. In this study, a beta-(1 -> 4)/beta-(1 -> 3)-linked glucosyl decasaccharide is experimentally investigated by synchrotron small-angle X-ray scattering from which its radius of gyration (R-g) is obtained. Molecular dynamics (MD) simulations of the decasaccharide show four populated states at each glycosidic linkage, namely, syn- and anti-conformations. The calculated R-g values from the MD simulation reveal that in addition to syn-conformers the presence of anti-psi conformational states is required to reproduce experimental scattering data, unveiling inherent glycosidic linkage flexibility. The CHARMM36 force field for carbohydrates thus describes the conformational flexibility of the decasaccharide very well and captures the conceptual importance that anti-conformers are to be anticipated at glycosidic linkages of carbohydrates.

  • 28.
    Jonker, Sybrand J. T.
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Diner, Colin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Schulz, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Iwamoto, Hiroaki
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Eriksson, Lars
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Szabó, Kálmán J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Catalytic asymmetric propargyl- and allylboration of hydrazonoesters: a metal-free approach to sterically encumbered chiral alpha-amino acid derivatives2018In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 54, no 91, p. 12852-12855Article in journal (Refereed)
    Abstract [en]

    A new asymmetric catalytic propargyl- and allylboration of hydrazonoesters is reported. The reactions utilize allenyl- and allylboronic acids in the presence of the inexpensive parent BINOL catalyst. The reactions can be performed under mild conditions (0 degrees C) without any metal catalyst or other additives affording sterically encumbered chiral -amino acids. This is the first metal-free method for the asymmetric propargyl- and allylboration of hydrazonoesters.

  • 29.
    Kazemi, Masoud
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sheng, Xiang
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kroutil, Wolfgang
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Computational Study of Mycobacterium smegmatis Acyl Transferase Reaction Mechanism and Specificity2018In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 8, no 11, p. 10698-10706Article in journal (Refereed)
    Abstract [en]

    The acyl transferase from Mycobacterium smegmatis (MsAcT) catalyzes the acyl transfer between a range of primary and secondary alcohols, whereby its outstanding ability is to perform this reaction in aqueous solution. Therefore, MsAcT opens different options for acylation reactions enabling alternatives for many conventionally hydrolytic enzymes used in biocatalysis. Nevertheless, hydrolysis is still a major side reaction of this enzyme. To provide a detailed understanding of the competition between hydrolysis and transesterification reactions, a combination of density functional theory and free energy perturbation methods have been employed. The relative binding free energies and the energy profiles of the chemical steps involved in the reaction were calculated for a number of substrates. The calculations show that the enzyme active site exhibits a higher affinity for substrates with an aromatic ring. The rate-determining step corresponds to the collapse of a negatively charged tetrahedral intermediate in the substrate acylation half-reaction. The intrinsic barriers of the transesterification and hydrolysis half-reactions are calculated to be of similar heights, suggesting that the determining factor in the MsAcT specificity is the higher binding affinity of the active site for the alcohol substrates relative to water. Finally, the influence of the acyl donor on the MsAcT-catalyzed reaction is also investigated by considering different esters in the calculations.

  • 30.
    Kazemi, Masoud
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry. Uppsala University, Sweden.
    Socan, Jaka
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Åqvist, Johan
    Mechanistic alternatives for peptide bond formation on the ribosome2018In: Nucleic Acids Research, ISSN 0305-1048, E-ISSN 1362-4962, Vol. 46, no 11, p. 5345-5354Article in journal (Refereed)
    Abstract [en]

    The peptidyl transfer reaction on the large ribosomal subunit depends on the protonation state of the amine nucleophile and exhibits a large kinetic solvent isotope effect (KSIE similar to 8). In contrast, the related peptidyl-tRNA hydrolysis reaction involved in termination shows a KSIE of similar to 4 and a pH-rate profile indicative of base catalysis. It is, however, unclear why these reactions should proceed with different mechanisms, as the experimental data suggests. One explanation is that two competing mechanisms may be operational in the peptidyl transferase center (PTC). Herein, we explored this possibility by re-examining the previously proposed proton shuttle mechanism and testing the feasibility of general base catalysis also for peptide bond formation. We employed a large cluster model of the active site and different reaction mechanisms were evaluated by density functional theory calculations. In these calculations, the proton shuttle and general base mechanisms both yield activation energies comparable to the experimental values. However, only the proton shuttle mechanism is found to be consistent with the experimentally observed pH-rate profile and the KSIE. This suggests that the PTC promotes the proton shuttle mechanism for peptide bond formation, while prohibiting general base catalysis, although the detailed mechanism by which general base catalysis is excluded remains unclear.

  • 31.
    Kervefors, Gabriella
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Becker, Antonia
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Dey, Chandan
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Olofsson, Berit
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Metal-free formal synthesis of phenoxazine2018In: Beilstein Journal of Organic Chemistry, ISSN 2195-951X, E-ISSN 1860-5397, Vol. 14, p. 1491-1497Article in journal (Refereed)
    Abstract [en]

    A transition metal-free formal synthesis of phenoxazine is presented. The key step of the sequence is a high-yielding O-arylation of a phenol with an unsymmetrical diaryliodonium salt to provide an ortho-disubstituted diaryl ether. This species was cyclized to acetylphenoxazine in moderate yield. The overall yield in the three-step sequence is 72% based on recovered diaryl ether. An interesting, unusually stable iodine(III) intermediate in the O-arylation was observed by NMR and could be converted to the product upon longer reaction time.

  • 32.
    Khanh Mai, Binh
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Szabó, Kálmán J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mechanisms of Rh-Catalyzed Oxyaminofluorination and Oxyaminotrifluoromethylthiolation of Diazocarbonyl Compounds with Electrophilic Reagents2018In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 20, no 21, p. 6646-6649Article in journal (Refereed)
    Abstract [en]

    Density functional theory calculations were performed to study the detailed reaction mechanisms of rhodium-catalyzed oxyaminofluorination and oxyaminotrifluoromethylthiolation of diazocarbonyl compounds with electrophilic N-F and N-SCF3-based reagents. The calculations show that the operating mechanisms for the two reactions are identical. The catalytic cycle starts with N-2 dissociation to provide a rhodium-carbene intermediate, followed by nucleophilic attack of tetrahydrofuran on the carbene and a rhodium coordination change generating a rhodium-enolate intermediate. Subsequent electrophilic attack introduces the fluorine or the SCF3 moiety, and it is followed by nucleophilic attack of the remaining amino group to yield the final product.

  • 33.
    Khanh Mai, Binh
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Szabó, Kálmán J.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine2018In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 8, no 5, p. 4483-4492Article in journal (Refereed)
    Abstract [en]

    The reaction mechanisms of rhodium-catalyzed geminal oxyfluorination and oxytrifluoromethylation of diazo-carbonyl compounds with fluoro-benziodoxole and Togni reagents are investigated by means of density functional theory calculations. It is shown that the two reactions follow very similar mechanisms, involving N-2 dissociation to form a Rh-carbene intermediate, alcohol insertion and proton transfer resulting in a stable Rh-enol intermediate, and concerted proton transfer/electrophilic addition of the hypervalent iodine reagent to the enol. Isomerization of the hypervalent iodine takes then place before a ligand coupling affords the final product. The role of the dirhodium catalyst in facilitating the various steps of the reaction is discussed. The presented mechanisms are consistent with available experimental information, and the obtained insights allow for extension to other reactions involving hypervalent iodine reagents.

  • 34. Kiss, Anita
    et al.
    Herman, Bianka Edina
    Görbe, Tamás
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Mernyak, Erzsebet
    Molnar, Barnabas
    Wolfling, Janos
    Szecsi, Mihaly
    Schneider, Gyula
    Synthesis of novel 17-triazolyl-androst-5-en-3-ol epimers via Cu(I)-catalyzed azide-alkyne cycloaddition and their inhibitory effect on 17 alpha-hydroxylase/ C-17,C-20-lyase2018In: Steroids, ISSN 0039-128X, E-ISSN 1878-5867, Vol. 135, p. 79-91Article in journal (Refereed)
    Abstract [en]

    The regioselective Cu(I)-catalyzed 1,3-dipolar cycloaddition of 17 alpha- and 17 beta-azidoandrost-5-en-3 beta-ol epimers (3b and 5b) with different terminal alkynes afforded novel 1,4-substituted triazolyl derivatives (8a-k and 9a-k). For the preparation of 5'-iodo-l',2',3'-triazoles (8m-n and 9m-n), an improved method was developed, directly from steroidal azides and terminal alkynes, in reaction mediated by Cul and IC1 as iodinating agents. Acetolysis and subsequent hydrolysis of 8n and 9n yielded 5'-hydroxy-l',2',3'-triazoles 8o and 9o. The inhibitory effect of 8a-o, 9a-o, 3, and 5 on rat testicular C-17,C-20-lyase was investigated by means of an in vitro radioincubation technique. The results revealed that the C-17 epimers of steroidal triazoles influence the C-17,C-20-lyase effect. Inhibitors were found only in the 17 alpha-triazolyl series (8a-o), whereas in the C-17 azide pair the 17 beta compound (5b) was more potent.

  • 35.
    Kumaniaev, Ivan
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Samec, Joseph S. M.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Valorization of Quercus suber Bark toward Hydrocarbon Bio-Oil and 4-Ethylguaiacol2018In: ACS sustainable chemistry and engineering, ISSN 2168-0485, Vol. 6, no 5, p. 5737-5742Article in journal (Refereed)
    Abstract [en]

    A reductive fractionation process for the valorization of Quercus suber bark toward hydrocarbons in gasoline and diesel ranges and optionally 4-ethylguaiacol has been developed. The procedure involves three steps: (1) tandem hydrogen-free Pd/C-catalyzed transfer hydrogenolysis of lignin where the carbohydrates serve as an inherent hydrogen donor under slightly alkaline conditions to also facilitate the depolymerization of suberin, (2) optional distillation, to isolate the 4-ethylguaiacol, (3) hydrodeoxygenation of the mixture from the first step by a Pt-MoO3/TiO2 catalyst generated hydrocarbons in gasoline and diesel ranges. The yield of 4-ethylguaiacol (90% purity) is 2.6% of dry bark weight (12% of acid insoluble lignin), and yield of hydrocarbon bio-oil is 42% of dry bark weight. This corresponds to a theoretical maximum yield of 77% for lignin and suberin. The carbon yield of the obtained bio-oil is thereby 64% from the total initial bark.

  • 36. Kärkäs, Markus D.
    et al.
    Li, Ying-Ying
    Siegbahn, Per E. M.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Liao, Rong-Zhen
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Metal-Ligand Cooperation in Single-Site Ruthenium Water Oxidation Catalysts: A Combined Experimental and Quantum Chemical Approach2018In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 57, no 17, p. 10881-10895Article in journal (Refereed)
    Abstract [en]

    Catalysts for oxidation of water to molecular oxygen are essential in solar-driven water splitting. In order to develop more efficient catalysts for this oxidatively demanding reaction, it is vital to have mechanistic insight in order to understand how the catalysts operate. Herein, we report the mechanistic details associated with the two Ru catalysts 1 and 2. Insight into the mechanistic landscape of water oxidation catalyzed by the two single-site Ru catalysts was revealed by the use of a combination of experimental techniques and quantum chemical calculations. On the basis of the obtained results, detailed mechanisms for oxidation of water by complexes 1 and 2 are proposed. Although the two complexes are structurally related, two deviating mechanistic scenarios are proposed with metal-ligand cooperation being an important feature in both processes. The proposed mechanistic platforms provide insight for the activation of water or related small molecules through nontraditional and previously unexplored routes.

  • 37.
    Lati, Monireh Pourghasemi
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry. University of Zanjan, Iran.
    Naeem, Muhammad Iqbal
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Alinia-Asli, Mokhtar
    Shirini, Farhad
    Rezvani, Mohammad Ali
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Johnston, Eric
    Verho, Oscar
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Palladium Nanoparticles Immobilized on an Aminopropyl-functionalized Silica-Magnetite Composite as a Recyclable Catalyst for Suzuki-Miyaura Reactions2018In: Chemistryselect, ISSN 2365-6549, Vol. 3, no 27, p. 7970-7975Article in journal (Refereed)
    Abstract [en]

    Herein, we describe the straightforward synthesis and thorough characterization of a magnetically-separable heterogeneous catalyst comprised of 1-3nm-sized Pd nanoparticles immobilized on a mesoporous silica-magnetite composite (Pd-0-AmP-SMC). Catalytic evaluations were conducted using Suzuki-Miyaura cross-couplings as the model reactions, for which this Pd nanocatalyst exhibited high performance in an environmentally-friendly solvent mixture. Additionally, this Pd nanocatalyst could be re-used up to five cycles without any observable loss of activity, and separation of the catalyst could be conveniently done by a magnet.

  • 38.
    Li, Man-Bo
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Inge, Andrew Kentaro
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Posevins, Daniels
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Gustafson, Karl P. J.
    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.
    Chemodivergent and Diastereoselective Synthesis of gamma-Lactones and gamma-Lactams: A Heterogeneous Palladium-Catalyzed Oxidative Tandem Process2018In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 44, p. 14604-14608Article in journal (Refereed)
    Abstract [en]

    A palladium-catalyzed oxidative tandem process of enallenols was accomplished within a homogeneous/heterogeneous catalysis manifold, setting the stage for the highly chemodivergent and diaster-eoselective synthesis of gamma-lactones and gamma-lactams under mild conditions.

  • 39.
    Liu, Jianguo
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Krajangsri, Suppachai
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Yang, Jianping
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Li, Jia-Qi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Andersson, Pher G.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Iridium-catalysed asymmetric hydrogenation of allylic alcohols via dynamic kinetic resolution2018In: Nature Catalysis, E-ISSN 2520-1158, Vol. 1, no 6, p. 438-443Article in journal (Refereed)
    Abstract [en]

    Dynamic kinetic resolutions (DKRs) allow for the conversion of both enantiomers of starting material into a single enantiomer  of product, hence avoiding the 50% yield limit observed in traditional kinetic resolutions. Transition-metal-catalysed variants have become an important and useful method in asymmetric synthesis. Here we report an asymmetric hydrogenation of allylic alcohols using an Ir–N,P-ligand complex via DKR. In contrast to the many DKRs involving carbonyl reduction, this methodology allows for DKR during alkene reduction. Mechanistic studies support the hypothesis that racemization of the substrate is achieved by cleavage and reforming of the oxygen–carbon bond. Under the cooperative dynamic kinetic asymmetric hydrogenation, a broad range of chiral alcohols containing two stereogenic centres were produced with excellent diastereoselectivities (up to 95:5) and enantioselectivities (up to 99%).

  • 40.
    Liu, Jie
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Ricke, Alexander
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Yang, Bin
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Bäckvall, Jan-E.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Efficient Palladium-Catalyzed Aerobic Arylative Carbocyclization of Enallenynes2018In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 57, no 51, p. 16842-16846Article in journal (Refereed)
    Abstract [en]

    Herein, we communicate a selective and efficient protocol for oxidative arylating carbocyclization of enallenynes using O-2 as the oxidant. The key to success for this aerobic transformation is the application of a specific electron transfer mediator (ETM), a bifunctional catalyst consisting of a metal-macrocycle and quinone moieties. This catalyst significantly facilitates the reoxidation of Pd-0 to Pd-II under atmospheric pressure of O-2. Diverse functionalized enallenynes react with aryl boronic acids to afford the corresponding cyclic tetraenes in moderate to good yields.

  • 41.
    Margarita, Cristiana
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Rabten, Wangchuk
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Andersson, Pher G.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Transition-Metal-Catalyzed Regioselective Asymmetric Mono-Hydrogenation of Dienes and Polyenes2018In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 32, p. 8022-8028Article in journal (Refereed)
    Abstract [en]

    Organic compounds containing multiple C=C bonds are attractive substrates for catalytic asymmetric hydrogenation. The full saturation of prochiral double bonds, controlling the creation of two or more stereocenters in one step, is obviously a remarkable goal. However, another fascinating and useful option is to selectively introduce a new defined stereogenic center while leaving other double bonds untouched. Thus, the retained functionalities can be further exploited in synthesis. Examples of regio- and enantioselective mono-hydrogenations of polyolefins are highlighted in this Concept article, and are divided according to the nature of the reduced double bond and the transition-metal catalyst used. Alkenes bearing coordinating functional groups are often preferentially hydrogenated by Rh- and Ru-complexes, while the more recently developed Ir-based catalysts promote the selective saturation on alkyl-substituted olefins. Relevant applications of this effective methodology in the synthesis of natural products are included to demonstrate its value in organic synthesis.

  • 42. Martínez-Gómez, Estrella
    et al.
    Ståhle, Jonas
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Gil-Ramírez, Yolanda
    Zúñiga-Ripa, Amaia
    Zaccheus, Mona
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Moriyón, Ignacio
    Iriarte, Maite
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Conde-Álvarez, Raquel
    Genomic Insertion of a Heterologous Acetyltransferase Generates a New Lipopolysaccharide Antigenic Structure in Brucella abortus and Brucella melitensis2018In: Frontiers in Microbiology, ISSN 1664-302X, E-ISSN 1664-302X, Vol. 9, article id 1092Article in journal (Refereed)
    Abstract [en]

    Brucellosis is a bacterial zoonosis of worldwide distribution caused by bacteria of the genus Brucella. In Brucella abortus and Brucella melitensis, the major species infecting domestic ruminants, the smooth lipopolysaccharide (S-LPS) is a virulence factor. This S-LPS carries a N-formyl-perosamine homopolymer O-polysaccharide that is the major antigen in serodiagnostic tests and is required for virulence. We report that the Brucella O-PS can be structurally and antigenically modified using wbdR, the acetyl-transferase gene involved in N-acetyl-perosamine synthesis in Escherichia coli O157:H7. Brucella constructs carrying plasmidic wbdR expressed a modified O-polysaccharide but were unstable, a problem circumvented by inserting wbdR into a neutral site of chromosome II. As compared to wild-type bacteria, both kinds of wbdR constructs expressed shorter O-polysaccharides and NMR analyses showed that they contained both N-formyl and N-acetyl-perosamine. Moreover, deletion of the Brucella formyltransferase gene wbkC in wbdR constructs generated bacteria producing only N-acetyl-perosamine homopolymers, proving that wbdR can replace for wbkC. Absorption experiments with immune sera revealed that the wbdR constructs triggered antibodies to new immunogenic epitope(s) and the use of monoclonal antibodies proved that B. abortus and B. melitensis wbdR constructs respectively lacked the A or M epitopes, and the absence of the C epitope in both backgrounds. The wbdR constructs showed resistance to polycations similar to that of the wild-type strains but displayed increased sensitivity to normal serum similar to that of a per R mutant. In mice, the wbdR constructs produced chronic infections and triggered antibody responses that can be differentiated from those evoked by the wild-type strain in S-LPS ELISAs. These results open the possibilities of developing brucellosis vaccines that are both antigenically tagged and lack the diagnostic epitopes of virulent field strains, thereby solving the diagnostic interference created by current vaccines against Brucella.

  • 43. Monti, Susanna
    et al.
    Srifa, Pemikar
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Kumaniaev, Ivan
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Samec, Joseph S. M.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    ReaxFF Simulations of Lignin Fragmentation on a Palladium-Based Heterogeneous Catalyst in Methanol-Water Solution2018In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 9, no 18, p. 5233-5239Article in journal (Refereed)
    Abstract [en]

    The interaction of fragments derived from lignin depolymerization with a heterogeneous palladium catalyst in methanol-water solution is studied by means of experimental and theoretical methodologies. Quantum chemistry calculations and molecular dynamics simulations based on the ReaxFF approach are combined effectively to obtain an atomic level characterization of the crucial steps of the adsorption of the molecules on the catalyst, their fragmentation, reactions, and desorption. The main products are identified, and the most important routes to obtain them are explained through extensive computational procedures. The simulation results are in excellent agreement with the experiments and suggest that the mechanisms comprise a fast chemisorption of identified fragments from lignin on the metal interface accompanied by bond breaking, release of some of their hydrogens and oxygens to the support, and eventual desorption depending on the local environment. The strongest connections are those involving the aromatic rings, as confirmed by the binding energies of selected representative structures, estimated at the quantum chemistry level. The satisfactory agreement with the literature, quantum chemistry data, and experiments confirms the reliability of the multilevel computational procedure to study complex reaction mixtures and its potential application in the design of high-performance catalytic devices.

  • 44.
    Olsén, Peter
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Morvan, Jennifer
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sawadjoon, Supaporn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Shatskiy, Andrey
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Johnston, Eric V.
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Cyclic allylic carbonates as a renewable platform for protecting chemistry in water2018In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 20, no 14, p. 3186-3190Article in journal (Refereed)
    Abstract [en]

    The present work explores different cyclic allylic carbonates as a potential class of allylcarbamate precursors. The 5-membered carbonate formed a carbamate with very good thermal and pH stability, which could be cleanly deprotected in aqueous solution, in just 30 min with 2 mol% Pd(OAc)(2) as catalyst. The polar nature of the installed motif made it possible to deprotect highly unpolar substrates in water as solvent.

  • 45.
    Olsén, Peter
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Oschmann, Michael
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Johnston, Eric V.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Åkermark, Björn
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Synthesis of highly functional carbamates through ring-opening of cyclic carbonates with unprotected alpha-amino acids in water2018In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 20, no 2, p. 469-475Article in journal (Refereed)
    Abstract [en]

    The present work shows that it is possible to ring-open cyclic carbonates with unprotected amino acids in water. Fine tuning of the reaction parameters made it possible to suppress the degree of hydrolysis in relation to aminolysis. This enabled the synthesis of functionally dense carbamates containing alkenes, carboxylic acids, alcohols and thiols after short reaction times at room temperature. When Glycine was used as the nucleophile in the ring-opening with four different five membered cyclic carbonates, containing a plethora of functional groups, the corresponding carbamates could be obtained in excellent yields (> 90%) without the need for any further purification. Furthermore, the orthogonality of the transformation was explored through ring-opening of divinylenecarbonate with unprotected amino acids equipped with nucleophilic side chains, such as serine and cysteine. In these cases the reaction selectively produced the desired carbamate, in 70 and 50% yield respectively. The synthetic design provides an inexpensive and scalable protocol towards highly functionalized building blocks that are envisioned to find applications in both the small and macromolecular arena.

  • 46. Orebom, Alexander
    et al.
    Verendel, J. Johan
    Samec, Joseph S. M.
    Stockholm University, Faculty of Science, Department of Organic Chemistry. RenFuel AB, Sweden.
    High Yields of Bio Oils from Hydrothermal Processing of Thin Black Liquor without the Use of Catalysts or Capping Agents2018In: ACS omega, ISSN 2470-1343, Vol. 3, no 6, p. 6757-6763Article in journal (Refereed)
    Abstract [en]

    Black liquor (BL) from the kraft pulping process has been treated at elevated temperatures (380 degrees C) in a batch reactor to give high yields of a bio oil comprising monomeric phenolic compounds that were soluble in organic solvents and mineral oil and a water fraction with inorganic salts. The metal content in the product was < 20 ppm after a simple extraction step. A correlation between concentration, temperature, and reaction time with respect to yield of desired product was found. At optimal reaction conditions (treating BL with 16 wt % dry substance at 380 degrees C for 20 min), the yield of extractable organics was around 80% of the original lignin with less than 7% of char. The product was analyzed by gel permeable chromatography, mass spectroscopy, nuclear magnetic resonance, elemental analysis, and inductively coupled plasma. It was found that a large fraction composed of mainly cresols, xylenols, and mesitols. This process provides a pathway to convert a major waste stream from a pulp mill into a refinery feed for fuel or chemical production, whereas at the same time the inorganic chemicals are recovered and can be returned back to the pulp mill.

  • 47.
    Pathipati, Stalin R.
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    van der Werf, Angela
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Selander, Nicklas
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Diastereoselective Synthesis of Polycyclic Indolizines with 2-(2-Enynyl)pyridines and Enamines2018In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 20, no 12, p. 3691-3694Article in journal (Refereed)
    Abstract [en]

    A diastereoselective metal-catalyzed reaction of 2-(2-enynyl)pyridines and cyclic enamines is reported. The method provides access to a variety of substituted indolizine derivatives by variation of the enyne component and the reaction conditions. Performing the reaction using a preformed enamine led to the formation of polycyclic indolizines. With in situ generated enamines, ketone-containing indolizine derivatives were obtained. An asymmetric reaction of 2-(2-enynyl)pyridines and enamines generated from an aldehyde and a catalytic amount of amine is presented.

  • 48.
    Planas, Ferran
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Sheng, Xiang
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    McLeish, Michael J.
    Himo, Fahmi
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    A Theoretical Study of the Benzoylformate Decarboxylase Reaction Mechanism2018In: Frontiers in Chemistry, E-ISSN 2296-2646, Vol. 6, article id 205Article in journal (Refereed)
    Abstract [en]

    Density functional theory calculations are used to investigate the detailed reaction mechanism of benzoylformate decarboxylase, a thiamin diphosphate (ThDP)-dependent enzyme that catalyzes the nonoxidative decarboxylation of benzoylformate yielding benzaldehyde and carbon dioxide. A large model of the active site is constructed on the basis of the X-ray structure, and it is used to characterize the involved intermediates and transition states and evaluate their energies. There is generally good agreement between the calculations and available experimental data. The roles of the various active site residues are discussed and the results are compared to mutagenesis experiments. Importantly, the calculations identify off-cycle intermediate species of the ThDP cofactor that can have implications on the kinetics of the reaction.

  • 49.
    Ponra, Sudipta
    et al.
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Rabten, Wangchuk
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Yang, Jianping
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Wu, Haibo
    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.
    Diastereo- and Enantioselective Synthesis of Fluorine Motifs with Two Contiguous Stereogenic Centers2018In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 42, p. 13878-13883Article in journal (Refereed)
    Abstract [en]

    The synthesis of chiral fluorine containing motifs, in particular, chiral fluorine molecules with two contiguous stereogenic centers, has attracted much interest in research due to the limited number of methods available for their preparation. Herein, we report an atom-economical and highly stereoselective synthesis of chiral fluorine molecules with two contiguous stereogenic centers via azabicyclo iridium-oxazoline-phosphine-catalyzed hydrogenation of readily available vinyl fluorides. Various aromatic, aliphatic, and heterocyclic systems with a variety of functional groups were found to be compatible with the reaction and provide the highly desirable product as single diastereomers with excellent enantioselectivities.

  • 50. Pope, Giovanna M.
    et al.
    Hung, Ivan
    Gan, Zhehong
    Mobarak, Hani
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Widmalm, Göran
    Stockholm University, Faculty of Science, Department of Organic Chemistry.
    Harper, James K.
    Exploiting C-13/N-14 solid-state NMR distance measurements to assign dihedral angles and locate neighboring molecules2018In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 54, no 49, p. 6376-6379Article in journal (Refereed)
    Abstract [en]

    The RESPDOR NMR method rapidly provides multiple C-13/N-14 distance measurements in natural abundance solids. In this study, C-13/N-14 RESPDOR information is shown, for the first time, to provide accurate molecular conformation and to locate non-bonded neighboring molecules.

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