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  • 1.
    Durieux, Guillaume
    et al.
    CNRS, Ecole Normale Super, Dept Chim.
    Gerdin, Martin
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Jutand, Anny
    CNRS, Ecole Normale Super, Dept Chim.
    Rate and Mechanism of the Oxidative Addition of a Silylborane to Pt0 Complexes: Mechanism for the Pt-Catalyzed Silaboration of 1,3-Cyclohexadiene2008In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 27, p. 4236-4241Article in journal (Refereed)
    Abstract [en]

    The chemical reduction of Pt(acac)(2) by DIBALH in the presence of phosphanes, which is used to generate active Pt-0 complexes in the Pt-catalyzed silaboration of cyclohexadiene by 2-(diinethylphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1) leading to the 1,4-silaborated product, was mimicked by the electrochemical reduction of Pt(acac)(2) in the presence of 2 equiv. of PR3 (R = Ph, nBu). The electrochemical reduction generates free acac anions and neutral Pt-0-(PR3)(2) complexes. The kinetics of the oxidative addition of bromobenzene (used first as a model molecule) and silylborane 1 to the Pt-0 complexes was investigated and the rate constants determined. Pt-0(PnBu(3))(2) is much more reactive than Pt-0(PPh3)(2) towards 1. From the electrochemical study, it emerges that the acac anions released in the reduction of Pt(acac)(2) do not coordinate to the Pt-0(PR3)(2) complexes. Consequently, the rate of the oxidative addition of 1 to Pt-0(PR3)(2), generated either by the electrochemical reduction or by the chemical reduction by DIBALH, is not affected by the acac anions and a posteriori not by aluminum cations. The oxidative addition and the further step of the catalytic cycle [insertion of the diene into the Pt-B bond of the Si-Pt-B complex generated in the oxidative addition, with formation of the eta(3)-allyl)Pt-Si complex] were monitored by NMR spectroscopy. Pt-0 and Pt-II complexes involved in the catalytic cycle were characterized. The oxidative addition is faster when the ligand is PMe2Ph relative to that obtained with PPh3, in agreement with the electrochemical data. No reductive elimination within the ((eta(3)-allyl))Pt-Si complex is observed when the ligand is PMe2Ph, whereas reactions in the presence of PPh3 proceeded to give the final product. As a consequence, PPh3 is a better ligand than PMe2Ph for the catalytic reaction, as observed experimentally.

  • 2.
    Gerdin, Martin
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Silaborations of Unsaturated Compounds2008Doctoral thesis, comprehensive summary (Other scientific)
    Abstract [en]

    This thesis deals with the development of transition metal-catalyzed silaborations of 1,3-dienes and 1,6-enynes.

    The first part of the thesis describes the development of the enantioselective 1,4-silaboration of 1,3-cyclohexadiene. A number of chiral metal-ligand complexes were evaluated. Up to 82% enantiomeric excess was obtained using a catalyst system derived from Pt(acac)2 and a phosphoramidite ligand. The product formed was employed in allylborations of aldehydes, giving homo-allylic alcohols in good yields with good to moderate diastereoselectivity. In attempts to widen the scope of silaborations to include acyclic, terminally substituted 1,3-dienes, products from H-B exchange with, and H-Si addition to, the dienes were obtained.

    The second part describes the development of silaborative carbocyclization of 1,6-enynes. A Pd N-heterocylic carbene complex was found to be effective for the silaborative carbocyclization of unsubstituted enynes, giving the products in good to excellent yields. Employing terminally substituted enynes resulted in low or no yields.

    The last part describes investigations into the reaction mechanisms of the processes developed in the first part. It was found that the silylborane undergoes oxidative addition to a Pt(0) complex generated from Pt(acac)2 and DIBALH. After insertion of 1,3-cyclohexadiene into the Pt-B bond a π-allyl complex was observed experimentally. In the addition of silylborane to acyclic, terminally substituted, 1,3-dienes it was shown by deuterium labeling experiments that one diene loses a hydride via H-B exchange and that this hydride is then added to another diene via H-Si addition. A reaction mechanism was proposed for this process.

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  • 3.
    Gerdin, Martin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Enantioselective Platinum-Catalyzed Silicon-Boron Addition to 1,3-Cyclohexadiene2005In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 347, no 6, p. 749-753Article in journal (Refereed)
    Abstract [en]

    Silaboration of 1,3-cyclohexadiene in the presence of Pt(acac)(2), DIBALH, and a phosphoramidite prepared from (S)-1,1'-bi-2-naphthol and diisopropylamine led to (1R,4S)-1-(dimethylphenylsilyl)4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene with 70% ee. Chiral catalysts based on Ni gave no or essentially racemic product, whereas complexes containing Pd were inactive.

     

     

     

     

  • 4.
    Gerdin, Martin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Ni-Catalyzed Si-B Addition to 1,3-Dienes: Disproportionation in Lieu of Silaboration2006In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 8, no 14, p. 2929-2932Article in journal (Refereed)
    Abstract [en]

    Upon attempted silaboration of acyclic 1- and 1,4-substituted 1,3-dienes, a new disproportionation reaction was discovered, yielding 1:1 mixtures of allylsilanes and dienylboranes. It was demonstrated that, as a key step in this new catalytic process, hydrogen is being transferred from one diene moiety to another.

  • 5.
    Gerdin, Martin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Silaborative Carbocyclization of 1,6-EnynesManuscript (Other academic)
    Abstract [en]

    The silaboration of 1,6-enynes gives densely functionalized five-membered rings that offer promising reactivities for further synthetic manipulations. We have found that using silylborane 4 silaborative carbocyclization reactions proceed in good to excellent yields, giving the product as a single diastereomer. Attempts to extend this methodology to include terminally substituted enynes and developing asymmetric versions were largely unsuccessful. The vinylboronates formed were employed in Suzuki cross-coupling reactions with a range of aryl bromides, furnishing arylated product in good yields.

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  • 6.
    Gerdin, Martin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Nadakudity, Sailendra Kumar
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Worch, Christin
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Regioselective Preparation of Functionalized exo-Methylene-cyclopentanes and exo-Methylenepyrrolidines via Silaborative Carbocyclization of 1,6-Enynes2010In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 352, no 14-15, p. 2559-2570Article in journal (Refereed)
    Abstract [en]

    Silaborative carbocyclization of 1,6-enynes catalyzed by Pd-PEPPSI-IPr {PEPPSI=pyridine-enhanced precatalyst preparation stabilization and initiation; IPr=N,N-bis[2,6-(diisopropyl)phenyl] imidazolium} employing either (dimethylphenylsilyl) pinacolborane or (chlorodimethylsilyl)pinacolborane provides access to densely functionalized five-membered rings as single diastereomers in excellent yields. The vinylboronate functions were employed in palladium-catalyzed Suzuki cross-coupling reactions with a range of aryl bromides, containing electron-with-drawing as well as electron-donating substituents, furnishing arylated exo-methylenecyclopentanes or exo-methylenepyrrolidines in good yields. Subsequent oxidation of the isopropoxydimethylsilyl function generated via addition of (chlorodimethylsilyl)-pinacolborane provided access to hydroxymethyl derivatives of the arylated compounds. Use of a chiral ester, bismenthyl (2-propenyl)(2-propynyl)malonate, afforded two diastereomeric products which could be separated, thereby giving access to the cyclized compounds as single isomers, with opposite absolute configurations at the newly formed stereocenter.

  • 7.
    Gerdin, Martin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Penhoat, Maël
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Zalubovskis, Raivis
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Pétermann, Claire
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Enantioselective silicon-boron additions to cyclic 1,3-dienes catalyzed by the platinum group metal complexes2008In: Journal of Organometallic Chemistry, ISSN 0022-328X, E-ISSN 1872-8561, Vol. 693, no 23, p. 3519-3526Article in journal (Refereed)
    Abstract [en]

    Silaborations of 1,3-cyclohexadiene and 1,3-cycloheptadiene were achieved using catalysts prepared from different combinations of phosphorus ligands and group 10 metal compounds. For the six-membered compound, 1,4-adducts with up to 82% ee were obtained employing Pt(0) and phosphoramidite ligands. For the seven-membered diene optimal conditions were found using catalysts based on Ni(0), but the highest selectivity observed was merely 22% ee. No improvement of the chiral induction was obtained using chiral silylboranes in combination with chiral phosphoramidite ligands in the additions to 1,3-cyclohexadiene. The adduct obtained from cyclohexadiene was used in allylborations of aldehydes under microwave irradiation to produce homoallylic alcohols with moderate to good diastereoselectivity.

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