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  • 1. Alonso, D A
    et al.
    Bertilsson, S K
    Johnsson, S Y
    Nordin, S J M
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Södergren, M J
    Andersson, Pher G
    New Expidient Route to Both Enantiomers of Nonproteinogenic Amino Acid Derivatives from the Unsaturated 2-Aza-bicyclo Moiety. D. A1999In: J. Org. Chem., Vol. 64, p. 2276-Article in journal (Refereed)
  • 2. Alonso, D A
    et al.
    Nordin, S J M
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Andersson, Pher G
    Highly Diastereoselective Reaction of 2-Azanorbornyl Enolates with Electrophiles. D. A1999In: Org. Lett., Vol. 1, p. 1595-Article in journal (Refereed)
  • 3. Alonso, D A
    et al.
    Nordin, S J M
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Roth, P
    Tarnai, T
    Thommen, M
    Pittelkow, U
    Andersson, Pher G
    2-Azanorbornyl alcohols: Very efficient Ligands for Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of Aromatic Ketones. D. A1999In: J. Org. Chem., Vol. 65, p. 3116-Article in journal (Refereed)
  • 4.
    Alonso, Diego A
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Brandt, P
    Nordin, Sofia J M
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Andersson, Pher G
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Ru(arene)(amino alcohol)-Catalyzed Transfer Hydrogenation of Ketones: Mechanism and Origin of Enantioselectivity1999In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 121, no 41, p. 9580-9588Article in journal (Refereed)
    Abstract [en]

    The mechanism of the Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones using isopropyl alcohol as the hydrogen source has been studied by means of hybrid density functional methods (B3PW91). Three mechanistic alternatives were evaluated, and it was shown that the reaction takes place via a six-membered transition state, where a metal-bound hydride and a proton of a coordinated amine are transferred simultaneously to the ketone. Further calculations provided a general rationale for the rate of the reaction by comparison of steric effects in the ground and transition states of the ruthenium hydride complex. It was found that the TS has a strong preference for planarity, and this in turn is dependent on the conformational behavior of the O,N-linkage of the amino alcohol ligand. Finally, a general model, rationalizing the enantioselectivity of the reaction, was developed. Experimental studies of both rate and enantioselectivity were used in order to support the computational results.

  • 5.
    Arnaud, Gayet
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Christelle, Bolea
    Pher G., Andersson
    Development of new camphor based N,S chiral ligands and their application in transfer hydrogenation2004In: Organic & Biomolecular Chemistry, ISSN 1477-0520, Vol. 2, no 13, p. 1887-1893Article in journal (Refereed)
  • 6.
    Arnaud, Gayet
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Sophie, Bertilsson
    Pher G., Andersson
    Novel Catalytic Kinetic Resolution Of Racemic Epoxides to Allylic alcohols2002In: Organic Letters, ISSN 1523-7060, Vol. 4, no 22, p. 3777-3779Article in journal (Refereed)
  • 7.
    Bergman, Jan
    et al.
    CNT, DEPT ORGAN CHEM, S-14157 HUDDINGE, SWEDEN .
    Lidgren, Göran
    ROYAL INST TECHNOL, DEPT ORGAN CHEM, S-10044 STOCKHOLM 70, SWEDEN.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Synthesis and Reactions of Oxazolones from L‑Tryptophan and α‑Haloacetic Anhydrides1992In: Bulletin des Sociétés chimiques belges, ISSN 0037-9646, Vol. 101, no 7, p. 643-660Article in journal (Refereed)
    Abstract [en]

    Optically active 5(4H)-oxazolones have been synthesized from L-tryptophan and an excess of trifluoro-, trichloro-, and dichloroacetic anhydrides. Some of the 5(4H)-xazolones have been further transformed to the isomeric 5(2H)-oxazolones as well as oxazolones with exocyclic double bonds. Treatment of the various oxazolones under hydrolytic, acidic and Friedel-Crafts acylation conditions gave indole-3-pyruvic acid, alpha,beta-dehydrotryptophans, beta-carbolines as well as the functionalized cyclopentanoindole 32. Treatment of the 4-(3-indolylmethyl)-2-trifluoromethyl-5(2H)-oxazolone (17) with trifluoroacetic acid gave the 3,4-bridged azepinoindole 35.

  • 8.
    Bergström, Sara K.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Analytical Chemistry.
    Edenwall, Niklas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Analytical Chemistry.
    Lavén, Martin
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Analytical Chemistry.
    Velikyan, Irina
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Långström, Bengt
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Markides, Karin E.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Analytical Chemistry.
    Polyamine deactivation of integrated poly(dimethylsiloxane) structures investigated by radionuclide imaging and capillary electrophoresis experiments2005In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 77, no 3, p. 938-942Article in journal (Refereed)
    Abstract [en]

    The poly(dimethylsiloxane) (PDMS) material provides a number of advantageous features, such as flexibility, elasticity, and transparency, making it useful in integrated analytical systems. Hard fused-silica capillary structures and soft PDMS channels can easily be combined by a tight fit, which offers many alternatives for structure combinations. PDMS and fused silica are in different ways prone to adsorption of low levels of organic compounds. The need for modification of the inner wall surface of PDMS channels may often be necessary, and in this paper, we describe an easy and effective method using the amine-containing polymer PolyE-323 to deactivate both fused-silica and PDMS surfaces. The adsorption of selected peptides to untreated surfaces was compared to PolyE-323-modified surfaces, using both radionuclide imaging and capillary electrophoresis experiments. The polyamine modification displayed a substantially reduced adsorption of three hydrophobic test peptides compared to the native PDMS surface. Filling and storage of aqueous solution were also possible in PolyE-323-modified PDMS channels. In addition, hybrid microstructures of fused silica and PDMS could simultaneously be deactivated in one simple coating procedure.

  • 9. Berlin, Stefan
    et al.
    Ericsson, Cecilia
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Engman, Lars
    Construction of Tetrahydrofuran-3-ones from Readily Available Organochalcogen Precursors via Radical Carbonylation/Reductive Cyclization2002In: Organic Letters, Vol. 4, p. 3-Article in journal (Refereed)
  • 10. Berlin, Stefan
    et al.
    Ericsson, Cecilia
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Engman, Lars
    Radical Carbonylation/Reductive Cyclization for the Construction of Tetrahydrofuran-3-ones and Pyrrolidin-3-ones2003In: Journal of Organic Chemistry, Vol. 68, p. 8386-Article in journal (Refereed)
  • 11.
    Beşev, Magnus
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Radical Cyclization Approaches to Pyrrolidines2002Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Five-membered rings are readily prepared by 5-exo-trig radical cyclization. This thesis is concerned with novel methodology for pyrrolidine synthesis. We have synthesised selenium containing radical precursors from aziridines and α-phenylseleno ketones, and cyclized them to 2,4- and 3,4-disubstituted pyrrolidines. A few examples of 5-exo-dig cyclization were also demonstrated. In another study we investigated the capacity of the nitrogen protecting group to direct diastereoselectivity in the formation of 2,4-disubstituted pyrrolidines. The diphenylphosphinoyl protecting group directed cyclization to occur in a highly cis-selective manner. When cyclizations were performed at 17 oC, cis/trans-ratios as high as 24/1 were obtained. In contrast, cyclization of the unprotected pyrrolidine precursor afforded the trans-diastereomer as the major product (cis/trans = 1/3.3 – 1/20). We also examined the use of a hydroxyl auxiliary for controlling diastereoselectivity in radical cyclization. The required selenium containing radical precursors were synthesised from 2-cyanoaziridines by addition of organometallic reagents, reduction of the resulting aziridine ketone, and benzeneselenol ring-opening of the aziridine. Cyclization at 17 oC produced 2,4-disubstituted pyrrolidines substantially enriched in the trans-isomer (cis/trans = 1/9 – 1/12). Novel radical cyclization approaches to thiazolines and pyrrolines were also tried.

    The thesis also describes attempts to improve the Hassner aziridine synthesis by employing stannous chloride as a functional group tolerant reducing agent.

  • 12.
    Bäckvall, Jan-Erling
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Andersson, Pher
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Stone, Guy
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Gogoll, Adolf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Syntheses of (±)-α- and (±)- γ- Lycorane via a Stereocontrolled Organopalladium Route1991In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 56, no 9, p. 2988-2993Article in journal (Refereed)
    Abstract [en]

    Total syntheses of (+/-)-alpha-and (+/-)-gamma-lycorane are described. The key steps in the syntheses are the stereocontrolled palladium-catalyzed intramolecular 1,4-chloroamidation of 12 to 13 and the subsequent anti-stereoselective copper-catalyzed S(N)2' reaction of allylic chloride 13 with [3,4-(methylenedioxy)phenyl]magnesium bromide to give 14. Hexahydroindole 14 has the required relative stereochemistry between carbons 3a, 7, and 7a for alpha-lycorane (1a) and was transformed to the latter via 15 and 16. The epimeric gamma-lycorane (2) was obtained by performing the Bischler-Napieralski cyclization on 14, which led to a highly stereoselective isomerization to give exclusively 17. Compound 17 was subsequently transformed to 2. The overall yield from ester 8 to (+/-)-alpha- and (+/-)-gamma-lycorane was 40 and 36%, respectively.

  • 13. Büttner, Frank
    et al.
    Norgren, Anna S.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Zhang, Suode
    Prabpai, Samran
    Kongsaeree, Palangpon
    Arvidsson, Per I.
    Cyclic β-tetra- and pentapeptides: Synthesis through on-resin cyclization and conformational studies by X-ray, NMR and CD spectroscopy and theoretical calculations2005In: Chemistry--A European Journal, ISSN 0947-6539, Vol. 11, no 21, p. 6145-6158Article in journal (Refereed)
  • 14.
    Diesen, Jarle Sidney
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Asymmetric Hydrogenations of Imines, Vinyl Fluorides, Enol Phosphinates and Other Alkenes Using N,P-Ligated Iridium Complexes2008Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    The research described in this thesis is directed toward the efficient, enantioselective synthesis of chiral products that have useful functionality. This goal was pursued through catalytic asymmetric hydrogenation, a reaction class that selectively introduces one or two stereocenters into a molecule in an atom-efficient step. This reaction uses a small amount (often <1 mol%) of a chiral catalyst to impart stereoselectivity to the product formed. Though catalytic asymmetric hydrogenation is not a new reaction type, there remain many substrate classes for which it is ineffective. The present thesis describes efforts to extend the reaction to some of these substrates classes. Some of the products synthesized in these studies may eventually find use as building blocks for the production of chiral pharmaceuticals, agrochemicals, or flavouring or colouring agents. However, the primary and immediate aim of this thesis was to develop and demonstrate new catalysts that are rapid and effective in the asymmetric hydrogenation of a broad range of compounds.

    Paper I describes the design and construction of two new, related chiral iridium compounds that are catalysts for asymmetric hydrogenation. They each contain an N,P-donating phosphinooxazoline ligand that is held together by a rigid bicyclic unit. One of these iridium compounds catalyzed the asymmetric hydrogenation of acyclic aryl imines, often with very good enantioselectivities. This is particularly notable because acyclic imines are difficult to reduce with useful enantioselectivity. The second catalyst was useful for the asymmetric hydrogenation of two aryl olefins. In Paper II, the class of catalysts introduced into Paper I is expanded to include many more related compounds, and these are also applied to the asymmetric hydrogenation of prochiral imines and olefins. By studying a range of related catalysts that differ in a single attribute, we were able to probe how different parts of the catalyst affect the yield and selectivity of the hydrogenation reactions.

    Whereas iridium catalysts had been applied to the asymmetric hydrogenation of imines and largely unfunctionalized olefins prior to this work (with varied degrees of success), they had not been used to reduce fluoroolefins. Their hydrogenation, which is discussed in Paper III, was complicated by concomitant defluorination to yield non-halogenated alkanes. To combat this problem, several iridium-based hydrogenation catalysts were applied to the reaction. Two catalysts stood out for their ability to produce chiral fluoroalkanes in good enantioselectivity while minimizing the defluorination reaction, and one of these bore a phosphinooxazoline ligand of the type described in Papers I and II.

    Enol phosphinates are another class of olefins that had not previously been subjected to iridium-catalyzed asymmetric hydrogenation. They do, however, constitute an attractive substrate class, because the product chiral alkyl phosphinates can be transformed into chiral alcohols or chiral phosphines with no erosion of enantiopurity. Iridium complexes of the phosphinooxazoline ligands described in Papers I and II were extremely effective catalysts for the asymmetric hydrogenation of enol phosphinates. They produced alkyl phosphinates from di- and trisubstituted enol phosphinate, β-ketoester-derived enol phosphinates, and even purely alkyl-substituted enol phopshinates, in very high yields and enantioselectivities.

    List of papers
    1. Application of Phosphine-Oxazoline Ligands in Ir-Catalyzed Asymmetric Hydrogenation of Acyclic Aromatic N-Arylimines
    Open this publication in new window or tab >>Application of Phosphine-Oxazoline Ligands in Ir-Catalyzed Asymmetric Hydrogenation of Acyclic Aromatic N-Arylimines
    2004 In: Organic Letters, Vol. 6, no 21, p. 3825-3827Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-97350 (URN)
    Available from: 2008-05-13 Created: 2008-05-13Bibliographically approved
    2. Hydrogenation of Imines and Olefins Using Phosphine-Oxazoline Iridium Complexes as Catalysts
    Open this publication in new window or tab >>Hydrogenation of Imines and Olefins Using Phosphine-Oxazoline Iridium Complexes as Catalysts
    2006 In: Chemistry-A European Journal, Vol. 12, no 8, p. 2318-2328Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-97351 (URN)
    Available from: 2008-05-13 Created: 2008-05-13Bibliographically approved
    3. Iridium-Catalyzed Asymmetric Hydrogenation of Fluorinated Olefins Using N,P-Ligands: A struggle with hydrogenolysis and selectivity
    Open this publication in new window or tab >>Iridium-Catalyzed Asymmetric Hydrogenation of Fluorinated Olefins Using N,P-Ligands: A struggle with hydrogenolysis and selectivity
    2007 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 129, no 15, p. 4536-4537Article in journal (Refereed) Published
    Abstract [en]

    To broaden the substrate scope of asymmetric iridium-catalyzed hydrogenation, fluorine-functionalized olefins were synthesized and hydrogenated with iridium complexes. Preliminary results showed high levels of fluorine elimination together with low selectivity. The loss of vinylic fluorine at first seemed difficult to handle, but further studies revealed that a catalyst with an azanorbornyl scaffold in the ligand gave more promising results. With this in mind, a new ligand was developed. This gave among the best results published to date for fluorine asymmetric hydrogenation, yielding high conversion and very high ee's with very little fluorine elimination. Further increasing the selectivity, the trials also revealed that tetrasubstituted fluorine-containing olefins can be hydrogenated with high ee's, despite that this class of compounds has usually shown low reactivity in this reaction type.

    National Category
    Chemical Sciences
    Identifiers
    urn:nbn:se:uu:diva-97352 (URN)10.1021/ja0686763 (DOI)000245739700016 ()17375924 (PubMedID)
    Available from: 2008-05-13 Created: 2008-05-13 Last updated: 2017-12-14Bibliographically approved
    4. Asymmetric Hydrogenation of Di and Trisubstituted Enol Phosphinates with N,P-Ligated Iridium Complexes
    Open this publication in new window or tab >>Asymmetric Hydrogenation of Di and Trisubstituted Enol Phosphinates with N,P-Ligated Iridium Complexes
    2008 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 130, no 16, p. 5595-5599Article in journal (Refereed) Published
    Abstract [en]

    The iridium-catalyzed asymmetric hydrogenation of various di- and trisubstituted enol phosphinates has been studied. Excellent enantioselectivities (up to >99% ee) and full conversion were observed for a range of substrates with both aromatic and aliphatic side chains. Enol phosphinates are structural analogues of enol acetates, and the hydrogenated alkyl phosphinate products can easily be transformed into the corresponding alcohols with conservation of stereochemistry. We have also hydrogenated, in excellent ee, several purely alkyl-substituted enol phosphinates, producing chiral alcohols that are difficult to obtain highly enantioselectively from ketone hydrogenations.

    National Category
    Chemical Sciences
    Identifiers
    urn:nbn:se:uu:diva-97722 (URN)10.1021/ja711372c (DOI)000255041400050 ()
    Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2017-12-14Bibliographically approved
  • 15. El-Sayed, Ibrahim
    et al.
    Guliashvili, Tamaz
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Hazell, Rita
    Gogoll, Adolf
    Ottosson, Henrik
    Evidence for Formation of Silenes Strongly Influenced by Reversed Si=C Bond Polarity2002In: Organic Letters, ISSN 1523-7060, Vol. 4, no 11, p. 1915-1918Article in journal (Refereed)
  • 16.
    Engman, Lars
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Al-Maharik, Nawaf
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    McNaughton, Michael
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Birmingham, A
    Uppsala University.
    Powis, G.
    Uppsala University.
    Thioredoxin Reductase and Cancer Cell Growth Inhibition by Organotellurium Compounds that could be Selectively Incorporated into Tumor Cells2003In: Bioorganic & Medicinal Chemistry, ISSN 0968-0896, E-ISSN 1464-3391, Vol. 11, no 23, p. 5091-5100Article in journal (Refereed)
    Abstract [en]

    The thioredoxins are small ubiquitous redox proteins with the conserved redox catalytic sequence-Trp-Cys-Gly-Pro-Cys-Lys, where the Cys residues undergo reversible NADPH dependent reduction by selenocysteine containing flavoprotein thioredoxin reductases. Thioredoxin expression is increased in several human primary cancers including lung, colon, cervix, liver, pancreatic, colorectal and squamous cell cancer. The thioredoxin/thioredoxin reductase pathway therefore provides an attractive target for cancer drug development. Organotellurium steroid, lipid, amino acid, nucleic base, and polyamine inhibitors were synthesized on the basis that they might be selectively or differentially incorporated into tumor cells. Some of the newly prepared classes of tellurium-based inhibitors (lipid-like compounds 3b and 3e, amino acid derivative 5b, nucleic base derivative 8b, and polyamine derivatives 14a and 14b) inhibited TrxR/Trx and cancer cell growth in culture with IC(50) values in the low micromolar range.

  • 17.
    Engman, Lars
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    McNaughton, Michael
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Gajewska, Malgorzata
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Kumar, Sangit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Birmingham, Anne
    Powis, Garth
    Thioredoxin reductase and cancer cell growth inhibition by organogold(III) compounds2006In: Anti-Cancer Drugs, ISSN 0959-4973, E-ISSN 1473-5741, Vol. 17, no 5, p. 539-544Article in journal (Refereed)
    Abstract [en]

    Thioredoxin (Trx) expression is increased in several human primary cancers associated with aggressive tumor growth and decreased patient survival, and the Trx/Trx reductase (TrxR) system therefore provides an attractive target for cancer drug development. Various gold(III) compounds with none, one, two or three carbon-gold bonds were evaluated for their capacity to inhibit TrxR and the growth of MCF-7 cancer cells in vitro. Compounds with up to two carbon-gold bonds were often potent inhibitors of TrxR with IC50 values as low as 2 nmol/l. In the presence of Trx and insulin the inhibiting capacity was much lower. However, the inhibitory concentrations of the compounds did not correlate with the ability to kill cells. Out of the organometallics tested, only compound 8 with two carbon-gold bonds was able to inhibit colony formation by MCF-7 breast cancer cells at low micromolar concentrations (IC50=1,6umol/l). Unfortunately, the compound did not show any anti-tumor activity against MCF-7 breast cancer and HT-29 colon cancer zenografts in scid mice.

  • 18.
    Erdélyi, Máté
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Towards the Development of Photoswitchable β-Hairpin Mimetics2004Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Peptide secondary structure mimetics are important tools in medicinal chemistry, as they provide analogues of endogeneous peptides with new physicochemical and pharmacological properties. The β-hairpin motif has been shown to be involved in numerous physiological processes, among others in regulation of eucariotic gene transcription. This thesis addresses the design, synthesis and conformational analysis of photoswitchable β-hairpin mimetics.

    The developmental work included the establishment of an improved procedure for cross coupling of aryl halides with terminal alkynes. Microwave mediated Sonogashira couplings in closed vessels were optimized under homogeneous and solid-phase conditions furnishing excellent yields for a large variety of substrates within 5 – 25 minutes. In addition, microwave heating was shown not to have any non-conventional effect on the reaction rate.

    Furthermore, the most important factors affecting β-hairpin stability were evaluated. Studies of tetrapeptide and decapeptide analogues revealed the essential role of the β-turn in initiation of hairpin folding. Moreover, hydrogen bonding was shown to be the main interchain stabilizing force, whereas hydrophobic interactions were found to be relatively weak. Nevertheless, hydrophobic packing appears to provide an important contribution to the thermodynamic stability of β-hairpins.

    Photoswitchable peptidomimetics were prepared by incorporation of various stilbene moieties into tetra- and decapeptides. Synthesis, photochemical isomerisation and spectroscopic conformational analysis of the compounds were performed.

    List of papers
    1. Rapid Homogeneous-Phase Sonogashira Coupling Reactions Using Controlled Microwave Heating
    Open this publication in new window or tab >>Rapid Homogeneous-Phase Sonogashira Coupling Reactions Using Controlled Microwave Heating
    2001 In: Journal of Organic Chemistry, Vol. 66, no 12, p. 4165-4169Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-91463 (URN)
    Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
    2. Rapid Microwave Promoted Sonogashira Coupling Reactions on Solid Phase
    Open this publication in new window or tab >>Rapid Microwave Promoted Sonogashira Coupling Reactions on Solid Phase
    2003 (English)In: Journal of Organic Chemistry, Vol. 68, no 16, p. 6431-6434Article in journal (Refereed) Published
    Abstract [en]

    A microwave-enhanced, rapid, and efficient solidphase version of the Sonogashira reaction is presented. It has been applied to the coupling of aryl iodides and bromides with various acetylene derivatives giving excellent yields in 15 to 25 min. The scopes of homogeneous, solventless, and solid-phase conditions for Sonogashira coupling of aryl halides are compared.

    National Category
    Organic Chemistry
    Identifiers
    urn:nbn:se:uu:diva-91464 (URN)10.1021/jo034284s (DOI)
    Available from: 2004-03-11 Created: 2004-03-11 Last updated: 2011-01-05
    3. Insight into β-Hairpin Stability: A Structural and Thermodynamic Study of Diastereomeric β-Hairpin Mimetics
    Open this publication in new window or tab >>Insight into β-Hairpin Stability: A Structural and Thermodynamic Study of Diastereomeric β-Hairpin Mimetics
    2002 In: New Journal of Chemistry, Vol. 26, p. 834-843Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-91465 (URN)
    Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
    4. Synthesis and Conformational Analysis of Novel Stibene-type Peptidomimetics
    Open this publication in new window or tab >>Synthesis and Conformational Analysis of Novel Stibene-type Peptidomimetics
    Show others...
    Article in journal (Refereed) Submitted
    Identifiers
    urn:nbn:se:uu:diva-91466 (URN)
    Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
    5. Synthesis and Conformational Analysis of Novel β-Hairpin mimetics. Factors Affecting Stability and Incorporation of a Photoswitchable Dipeptide Mimic
    Open this publication in new window or tab >>Synthesis and Conformational Analysis of Novel β-Hairpin mimetics. Factors Affecting Stability and Incorporation of a Photoswitchable Dipeptide Mimic
    Article in journal (Refereed) Submitted
    Identifiers
    urn:nbn:se:uu:diva-91467 (URN)
    Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
  • 19.
    Erdélyi, Máté
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Gogoll, Adolf
    Rapid Homogeneous-Phase Sonogashira Coupling Reactions Using Controlled Microwave Heating2001In: Journal of Organic Chemistry, Vol. 66, no 12, p. 4165-4169Article in journal (Refereed)
  • 20.
    Erdélyi, Máté
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Gogoll, Adolf
    Rapid Microwave Promoted Sonogashira Coupling Reactions on Solid Phase2003In: Journal of Organic Chemistry, Vol. 68, no 16, p. 6431-6434Article in journal (Refereed)
    Abstract [en]

    A microwave-enhanced, rapid, and efficient solidphase version of the Sonogashira reaction is presented. It has been applied to the coupling of aryl iodides and bromides with various acetylene derivatives giving excellent yields in 15 to 25 min. The scopes of homogeneous, solventless, and solid-phase conditions for Sonogashira coupling of aryl halides are compared.

  • 21.
    Erdélyi, Máté
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Langer, Vratislav
    Karlén, Anders
    Gogoll, Adolf
    Insight into β-Hairpin Stability: A Structural and Thermodynamic Study of Diastereomeric β-Hairpin Mimetics2002In: New Journal of Chemistry, Vol. 26, p. 834-843Article in journal (Refereed)
  • 22.
    Erdélyi, Máté
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Nurbo, Johanna
    Niklason, Ida
    Karlén, Anders
    Gogoll, Adolf
    Synthesis and Conformational Analysis of Novel Stibene-type PeptidomimeticsArticle in journal (Refereed)
  • 23.
    Erdélyi, Máté
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Persson, Åsa
    Karlén, Anders
    Gogoll, Adolf
    Synthesis and Conformational Analysis of Novel β-Hairpin mimetics. Factors Affecting Stability and Incorporation of a Photoswitchable Dipeptide MimicArticle in journal (Refereed)
  • 24.
    Ericsson, Cecilia
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Synthesis of Tetrahydrofuran and Pyrrolidine Derivatives Utilising Radical Reactions: Organochalcogenides in Reductive, Carbonylative and Group-Transfer Cyclisation2004Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis describes free-radical reactions for the construction of tetrahydrofuran and pyrrolidine derivatives. The studies are concerned with (i) diastereoselectivity in radical cyclisation, (ii) construction of tetrahydrofuran-3-ones and pyrrolidin-3-ones via radical carbonylation/cyclisation and (iii) synthesis of tetrahydrofuran derivatives via group-transfer cyclisation of organochalcogen compounds.

    (i) Diastereoselectivity in the synthesis of tetrahydrofuran derivatives via radical cyclisation was controlled by addition of Lewis acids. In the synthesis of 2,4-disubstitued tetrahydrofurans, the trans-isomer was formed as the major product in the unperturbed reaction. Upon addition of trialkylalumiums the diastereoselectivity was reversed. In a similar fashion, exo/endo-diastereoselectivity in the synthesis of bicyclic 2,3,4-trisubstituted tetrahydrofurans could also be controlled.

    (ii) Procedures for construction of tetrahydrofuran-3-ones and pyrrolidin-3-ones were presented. Epoxides were ring-opened with benzeneselenolate or benzenetellurolate and the resulting β-hydroxyalkyl phenyl chalcogenides were vinylated using ethyl propiolate/NMM or E-1,2-bis(phenylsulfonyl)ethylene/NaH. The corresponding nitrogen analogues were accessed by N-vinylation of aziridines followed by benzeneselenolate ring-opening. The two types of organochalcogen radical precursors were then treated with TTMSS/AIBN under an atmosphere of carbon monoxide (80 atm) to afford tetrahydrofuran-3-ones and pyrrolidin-3-ones, respectively, in high yields.

    (iii) Microwaves were found to induce group-transfer cyclisation of β-allyloxyalkyl aryl chalcogenides. Short time heating (3-10 min) at 250 oC in ethylene glycol was required to obtain tetrahydrofuran derivatives in 60-91% yield.

    List of papers
    1. Diastereocontrol by Trialkylaluminums in the Synthesis of Tetrahydrofurans via Radical Cyclisation
    Open this publication in new window or tab >>Diastereocontrol by Trialkylaluminums in the Synthesis of Tetrahydrofurans via Radical Cyclisation
    2001 In: Organic Letters, Vol. 3, p. 3459-Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-91437 (URN)
    Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
    2. Construction of Tetrahydrofuran-3-ones from Readily Available Organochalcogen Precursors via Radical Carbonylation/Reductive Cyclization
    Open this publication in new window or tab >>Construction of Tetrahydrofuran-3-ones from Readily Available Organochalcogen Precursors via Radical Carbonylation/Reductive Cyclization
    2002 In: Organic Letters, Vol. 4, p. 3-Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-91438 (URN)
    Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
    3. Radical Carbonylation/Reductive Cyclization for the Construction of Tetrahydrofuran-3-ones and Pyrrolidin-3-ones
    Open this publication in new window or tab >>Radical Carbonylation/Reductive Cyclization for the Construction of Tetrahydrofuran-3-ones and Pyrrolidin-3-ones
    2003 In: Journal of Organic Chemistry, Vol. 68, p. 8386-Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-91439 (URN)
    Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
    4. Microwave-Assisted Group-Transfer Cyclisation of Organotellurium Compounds
    Open this publication in new window or tab >>Microwave-Assisted Group-Transfer Cyclisation of Organotellurium Compounds
    Article in journal (Refereed) Submitted
    Identifiers
    urn:nbn:se:uu:diva-91440 (URN)
    Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
  • 25.
    Ericsson, Cecilia
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Engman, Lars
    Diastereocontrol by Trialkylaluminums in the Synthesis of Tetrahydrofurans via Radical Cyclisation2001In: Organic Letters, Vol. 3, p. 3459-Article in journal (Refereed)
  • 26.
    Ericsson, Cecilia
    et al.
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Engman, Lars
    Microwave-Assisted Group-Transfer Cyclisation of Organotellurium CompoundsArticle in journal (Refereed)
  • 27.
    Eriksson, Jonas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Synthesis of 11C-labelled Alkyl Iodides: Using Non-thermal Plasma and Palladium-mediated Carbonylation Methods2006Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Compounds labelled with 11C (β+, t1/2 = 20.4 min) are used in positron emission tomography (PET), which is a quantitative non-invasive molecular imaging technique. It utilizes computerized reconstruction methods to produce time-resolved images of the radioactivity distribution in living subjects.

    The feasibility of preparing [11C]methyl iodide from [11C]methane and iodine via a single pass through a non-thermal plasma reactor was explored. [11C]Methyl iodide with a specific radioactivity of 412 ± 32 GBq/µmol was obtained in 13 ± 3% decay-corrected radiochemical yield within 6 min via catalytic hydrogenation of [11C]carbon dioxide (24 GBq) and subsequent iodination, induced by electron impact.

    Labelled ethyl-, propyl- and butyl iodide was synthesized, within 15 min, via palladium-mediated carbonylation using [11C]carbon monoxide. The carbonylation products, labelled carboxylic acids, esters and aldehydes, were reduced to their corresponding alcohols and converted to alkyl iodides. [1-11C]Ethyl iodide was obtained via palladium-mediated carbonylation of methyl iodide with a decay-corrected radiochemical yield of 55 ± 5%. [1-11C]Propyl iodide and [1-11C]butyl iodide were synthesized via the hydroformylation of ethene and propene with decay-corrected radiochemical yields of 58 ± 4% and 34 ± 2%, respectively. [1-11C]Ethyl iodide was obtained with a specific radioactivity of 84 GBq/mmol from 10 GBq of [11C]carbon monoxide. [1-11C]Propyl iodide was synthesized with a specific radioactivity of 270 GBq/mmol from 12 GBq and [1-11C]butyl iodide with 146 GBq/mmol from 8 GBq.

    Palladium-mediated hydroxycarbonylation of acetylene was used in the synthesis of [1-11C]acrylic acid. The labelled carboxylic acid was converted to its acid chloride and subsequently treated with amine to yield N-[carbonyl-11C]benzylacrylamide. In an alternative method, [carbonyl-11C]acrylamides were synthesized in decay-corrected radiochemical yields up to 81% via palladium-mediated carbonylative cross-coupling of vinyl halides and amines. Starting from 10 ± 0.5 GBq of [11C]carbon monoxide, N-[carbonyl-11C]benzylacrylamide was obtained in 4 min with a specific radioactivity of 330 ± 4 GBq/µmol.

    List of papers
    1. [C-11]methyl iodide from [C-11]methane and iodine using a non-thermal plasma method
    Open this publication in new window or tab >>[C-11]methyl iodide from [C-11]methane and iodine using a non-thermal plasma method
    2006 (English)In: Journal of labelled compounds & radiopharmaceuticals, ISSN 0362-4803, E-ISSN 1099-1344, Vol. 49, no 13, p. 1177-1186Article in journal (Refereed) Published
    Abstract [en]

    A method and an apparatus for preparing [C-11]methyl iodide from [C-11]methane and iodine in a single pass through a non-thermal plasma reactor has been developed. The plasma was created by applying high voltage (400 V/31 kHz) to electrodes in a stream of helium gas at reduced pressure. The [C-11]methane used in the experiments was produced from [C-11]carbon dioxide via reduction with hydrogen over nickel. [C-11]methyl iodide was obtained with a specific radioactivity of 412 +/- 32 GBq/mu mol within 6 min from approximately 24 GBq of [C-11]carbon dioxide. The decay corrected radiochemical yield was 13 +/- 3% based on [C-11]carbon dioxide at start of synthesis. [C-11]Flumazenil was synthesized via a N-alkylation with the prepared [C-11]methyl iodide.

    Keywords
    [C-11]methyl iodide, [C-11]methane, non-thermal plasma, specific radioactivity
    National Category
    Chemical Sciences
    Identifiers
    urn:nbn:se:uu:diva-94929 (URN)10.1002/jlcr.1135 (DOI)000242796700006 ()
    Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2017-12-14Bibliographically approved
    2. Synthesis of [1-11C]ethyl iodide from carbon monoxide and its application in alkylation reactions
    Open this publication in new window or tab >>Synthesis of [1-11C]ethyl iodide from carbon monoxide and its application in alkylation reactions
    2004 (English)In: Journal of Labelled Compounds and Radiopharmaceuticals, ISSN 0362-4803, Vol. 47, no 11, p. 723-731Article in journal (Refereed) Published
    National Category
    Natural Sciences
    Identifiers
    urn:nbn:se:uu:diva-94930 (URN)
    Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2015-09-24
    3. Synthesis of [1-C-11]propyl and [1-C-11]butyl iodide from [C-11]carbon monoxide and their use in alkylation reactions
    Open this publication in new window or tab >>Synthesis of [1-C-11]propyl and [1-C-11]butyl iodide from [C-11]carbon monoxide and their use in alkylation reactions
    2006 (English)In: Journal of labelled compounds & radiopharmaceuticals, ISSN 0362-4803, E-ISSN 1099-1344, Vol. 49, no 12, p. 1105-1116Article in journal (Refereed) Published
    Abstract [en]

    A method to prepare [1-C-11]propyl iodide and [1-C-11]butyl iodide from [C-11]carbon monoxide via a three step reaction sequence is presented. Palladium mediated formylation of ethene with [C-11]carbon monoxide and hydrogen gave [1-C-11]propionaldehyde and [1-C-11]propionic acid. The carbonylation products were reduced and subsequently converted to [1-C-11]propyl iodide. Labelled propyl iodide was obtained in 58 +/- 4% decay corrected radiochemical yield and with a specific radioactivity of 270 +/- 33 GBq/mu mol within 15 min from approximately 12 GBq of [C-11]carbon monoxide. The position of the label was confirmed by C-13-labelling and C-13-NMR analysis. [1-C-11]Butyl iodide was obtained correspondingly from propene and approximately 8 GBq of [C-11]carbon monoxide, in 34 +/- 2% decay corrected radiochemical yield and with a specific radioactivity of 146 +/- 20 GBq/mu mol. The alkyl iodides were used in model reactions to synthesize [O-propyl-1-C-11]propyl and [O-butyl-1-C-11]butyl benzoate. Propyl and butyl analogues of etomidate, a (beta-11-hydroxylase inhibitor, were also synthesized.

    Keywords
    [C-11]carbon monoxide, [1-C-11]propyl iodide, [1-C-11]butyl iodide, carbonylation, formylation, alkylation
    National Category
    Chemical Sciences
    Identifiers
    urn:nbn:se:uu:diva-94931 (URN)10.1002/jlcr.1119 (DOI)000242335900009 ()
    Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2017-12-14Bibliographically approved
    4. Synthesis of [11C]/[13C]acrylamides by palladium-mediated carbonylation
    Open this publication in new window or tab >>Synthesis of [11C]/[13C]acrylamides by palladium-mediated carbonylation
    2007 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 3, p. 455-461Article in journal (Refereed) Published
    Abstract [en]

    Two methods are presented for the synthesis of acrylamides labelled with C-11 (beta(+), t(1/2) = 20.4 min) and C-11 in the carbonyl position. In the first method, [1-C-11]acrylic acid is synthesised from [C-11]carbon monoxide by palladium-mediated hydroxy-carbonylation of acetylene. The labelled carboxylic acid is converted into the acyl chloride and subsequently treated with amine to yield N-benzyl[carbonyl(11)C]acrylamide, The second method utilizes [C-11]carbon monoxide in a palladium-mediated carbonylative cross-coupling of vinyl halides and amines. A higher radiochemical yield is achieved with the latter method and the amount of amine needed is decreased to 1/20. The C-11-labelled acrylamides were isolated in up to 81 % decay-corrected radiochemical yield. Starting from 10 +/- 0.5GBq of [C-11]carbon monoxide, N-benzyl[carbonyl-C-11]acrylamide was obtained in 4 min with a specific radioactivity of 330 +/- 4 GBq mu mol-(1). Co-labelling with C-11 and C-13 enabled confirmation of the labelled position by C-13 NMR spectroscopy.

    Keywords
    Carbonylation, Amides, Carbon monoxide, Isotopic labelling, Carbon-11, 11C, PET
    National Category
    Chemical Sciences
    Research subject
    Organic Chemistry
    Identifiers
    urn:nbn:se:uu:diva-98592 (URN)10.1002/ejoc.200600700 (DOI)000243600100007 ()
    Available from: 2009-02-27 Created: 2009-02-27 Last updated: 2017-12-13Bibliographically approved
    5. [1-11C]Ethyl iodide and [1-11C]propyl iodide in the synthesis of two potential NK1-receptor ligands and initial PET-imaging
    Open this publication in new window or tab >>[1-11C]Ethyl iodide and [1-11C]propyl iodide in the synthesis of two potential NK1-receptor ligands and initial PET-imaging
    Show others...
    (English)Manuscript (Other academic)
    National Category
    Medicinal Chemistry
    Identifiers
    urn:nbn:se:uu:diva-94933 (URN)
    Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2018-01-13
  • 28.
    Eriksson, Jonas
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Antoni, Gunnar
    Långström, Bengt
    Synthesis of [1-11C]ethyl iodide from carbon monoxide and its application in alkylation reactions2004In: Journal of Labelled Compounds and Radiopharmaceuticals, ISSN 0362-4803, Vol. 47, no 11, p. 723-731Article in journal (Refereed)
  • 29.
    Eriksson, Ludvig
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Transition Metal Mediated Transformations of Carboranes2003Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis describes the use of copper and palladium to mediate transformations of carboranes, especially p-carborane.

    1-(1-p-carboranyl)-N-methyl-N-(2-butyl)-3-isoquinolinecarboxamide, a carborane containing analogue of the peripheral benzodiazepine receptor (PBR) ligand PK11195, has been synthesised. A key step in the reaction is the copper (I) mediated coupling of p-carborane with ethyl 1-bromo-isoquinoline-3-carboxylate.

    p-Carborane has been arylated on the 2-B-atom in high yields, using the Suzuki–Miyaura reaction. Thus the reaction between 2-I-p-carborane and various arylboronic acids [1-naphthyl-, phenyl-, 4-MeO-C6H4-, 3-CH3CONH-C6H4-, 4-NC-C6H4-, 3-NO2-C6H4-], gave the corresponding 2-aryl-p-carboranes in DME solution when reacted in the presence of cesium fluoride and the catalytic Pd2(dba)3–dppb system. Under the same conditions, the boron-boron bond forming reaction of two p-carboranylboronic esters (2-[(pinacolato)boron]-p-carborane and 2-[(neopentyl glycolato)boron]-p-carborane) was also shown feasible.

    p-Carborane has been vinylated on the 2-B-atom in high yields by use of the Heck reaction. The coupling between 2-I-p-carborane and various styrenes [4-H-, 4-C6H4-, 4-Cl , 4-Br-, 4-NO2-, 4-CH3O- and 4 CH3 ] resulted in the formation of the correspondingtrans-β-(2-B-p-carboranyl) styrene in DMF solution when reacted in the presence of silver phosphate and the palladacycle Herrmann´s catalyst. The reaction was shown to proceed at higher rate with electron rich than with electron deficient olefins.

    The feasibility of palladium-catalysed isotopic exchange of an iodinated closo-carborane with a radioisotope of iodine has been studied. 2-I-p-carborane was selected as a model compound. It was shown, that such isotopic exchange is possible and provides a high yield (83 ± 4.2 %) during 40 min long reaction. The reaction conditions were optimised, and it was demonstrated that presence of the tetra n-butylammonium hydrogensulphate is important in order to stabilise catalyst and provide reproducibility of labelling. In this work we have modified the methodology and extended the application to a wider range of iodinated carboranes. By the use of Herrmann’s catalyst in toluene at 100 °C this [125I]-iodide labelling could be improved and extended. 2-I-p- 9-I-m-, 9-I-o-, 3-I-o-carborane, 1-phenyl-3-I-o-carborane and 1,2-diphenyl-3-I-o-carborane could be [125I]-iodide labelled in high to excellent yields within 5 minutes.This reported palladium catalyzed radio-iodination of the uncharged closo-carboranes might find use in pharmacokinetic studies of carborane derivatives.

  • 30.
    Fagerlund, Amelie
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Sunnerheim, Kerstin
    Dimberg, Lena H.
    Radical-scavenging and antioxidant activity of avenanthramides2009In: Food Chemistry, ISSN 0308-8146, E-ISSN 1873-7072, Vol. 113, no 2, p. 550-556Article in journal (Refereed)
    Abstract [en]

    Avenanthramides are amides of cinnamoyl-anthranilic acids and, among cereals, are exclusively found in oats. This study investigated the structure-antioxidant activities of 15 avenanthramides with different substitution patterns in the two aromatic rings, seven of which were new avenanthramides synthesised and characterised in this study. Radical-scavenging activity was tested as reactivity towards 1,1-diphenyl-2-picrylhydrazyl (DPPH-). The activity increased with the number of radical-stabilising groups ortho to the phenolic hydroxy group. Both aromatic rings were independently important for activity, while conjugation across the amide bond was of minor importance. Antioxidant activity was determined as inhibition of linoleic acid oxidation. In contrast to the radical-scavenging activity, antioxidant activity was observed for most avenanthramides, and also for compounds with only one hydroxy group in either of the aromatic rings. Compared with alpha-tocopherol, the avenanthramides protected linoleic acid from oxidation to a smaller extent initially, but the effect lasted for a longer time.

  • 31.
    Fast, K J
    et al.
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET.
    Bergström, M
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET.
    Hedberg, E
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET.
    Cheng, A
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    Lu, L
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET.
    Wu, F
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET.
    Bergström, E
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET.
    Tolmachev, Vladimir
    Långström, Bengt
    Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Medicine, Department of Radiology, Oncology and Radiation Science, Section of Nuclear Medicine and PET. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
    76-Br-bromodeoxyuridine marker with PET-preclinical validation studies1997In: Journal of labelled compounds & radiopharmaceuticals, ISSN 0362-4803, E-ISSN 1099-1344, Vol. 40, no 5, p. 391-393Article in journal (Refereed)
  • 32.
    Gayet, Arnaud
    Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
    Development of New Chiral Bicyclic Ligands: Applications in Catalytic Asymmetric Transfer Hydrogenation, Epoxidations, and Epoxide Rearrangements2005Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    This thesis describes the synthesis and application of new chiral bicyclic ligands and their application in asymmetric catalysis. The studies involved: [i] The development of novel chiral bicyclic amino sulfur ligands and their use in transfer hydrogenation. [ii] The development of the kinetic resolution of racemic epoxide through the use of chiral lithium amides. [iii] The synthesis and application of chiral bicyclic amine in the organocatalysed epoxidation of alkenes. [iv] Development and application of new chiral diamine ligands in the rearrangement of epoxides into allylic alcohols.

    [i] The preparation of two-series of amino thiol ligands based on the structure of camphor is described, together with their application in the iridium-catalysed asymmetric transfer hydrogenation of acetophenone using isopropanol as the hydrogen source. Excellent activity and good enantioselectivity have been achieved using 2 mol% of chiral ligand in combination with [IrCl(COD)]2.

    [ii] The chiral diamines (1S,3R,4R)-3-(pyrrolidine-1-ylmethyl)-2-aza-bicyclo[2.2.1]heptane and its (2R,5R)-dimethylpyrrolidine derivative were applied to the kinetic resolution of a variety of racemic 5-7 membered cycloalkene oxides with lithium diisopropylamide (LDA) as the bulk base. Using 5 mol% of the chiral diamines, both unreacted epoxides and allylic alcohols could be produced in enantiomeric excess up to 99%.

    [iii] The synthesis of chiral bicyclic amines and their use in the organocatalysed epoxidation of alkene has been described. Using a substoichiometric amount of the chiral amines and aldehydes as ligands precursors, with Oxone® as oxidant, a good activity but moderate enantioselectivity was observed for the epoxidation of trans-stilbene.

    [iv] The preparation of 6-substituted-7-bromo-aza-bicyclo[2.2.1]heptanes via nucleophilic addition of organocopper reagents to 3-bromo-1-azoniatricyclo[2.2.1.0]heptyle bromide has been described. These compounds have been utilised as chiral building blocks in the preparation of novel chiral diamine ligands, which have been successfully applied to the catalysed asymmetric rearrangement of epoxide into the corresponding allylic alcohol.

    List of papers
    1. Novel Catalytic Kinetic Resolution Of Racemic Epoxides to Allylic alcohols
    Open this publication in new window or tab >>Novel Catalytic Kinetic Resolution Of Racemic Epoxides to Allylic alcohols
    2002 In: Organic Letters, ISSN 1523-7060, Vol. 4, no 22, p. 3777-3779Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-92519 (URN)
    Available from: 2005-01-10 Created: 2005-01-10Bibliographically approved
    2. Development of new camphor based N,S chiral ligands and their application in transfer hydrogenation
    Open this publication in new window or tab >>Development of new camphor based N,S chiral ligands and their application in transfer hydrogenation
    2004 In: Organic & Biomolecular Chemistry, ISSN 1477-0520, Vol. 2, no 13, p. 1887-1893Article in journal (Refereed) Published
    Identifiers
    urn:nbn:se:uu:diva-92520 (URN)
    Available from: 2005-01-10 Created: 2005-01-10Bibliographically approved
    3. Synthesis of 6-Substituted 7-Bomoazabicyclo[2.2.1]heptanes via Nucleophilic Addition to 3-Bromo-1-azoniatricyclo[2.2.1.0]-heptane Bromide
    Open this publication in new window or tab >>Synthesis of 6-Substituted 7-Bomoazabicyclo[2.2.1]heptanes via Nucleophilic Addition to 3-Bromo-1-azoniatricyclo[2.2.1.0]-heptane Bromide