Catalytic stereoselective addition to alkynes. Borylation or silylation promoted by magnesia-supported iron oxide and cis-diboronation or silaboration by supported platinum nanoparticles

作者: Anish Khan , Abdullah M Asiri , Samia A Kosa , Hermenegildo Garcia , Abdessamad Grirrane

DOI: 10.1016/J.JCAT.2015.05.006

关键词:

摘要: Abstract Iron oxide nanoparticles supported on magnesia (FeO/MgO) have been prepared by NaBH4 reduction of Fe(SO4) MgO and spontaneous reoxidation upon storage. XPS FeO/MgO indicates the presence Fe(0) (16%) Fe(II) (84%) this solid. TEM images show that catalytically active is constituted iron about 25 nm dispersed fibrous MgO. in catalytic amounts triphenylphosphine promotes highly regio- stereoselective monoborylation aromatic, aliphatic, terminal internal alkynes. Chemical analysis liquid after reaction control experiments using salts absence or PPh3 supports catalysis heterogeneous. The possibility trace copper impurities present precursor influence activity was studied a commercially available high-purity as (99.999% Fe purity) showing again good (but lower) activity. In addition, experiment catalyst containing 30 times higher Cu than low purity did not lead to complete alkyne conversion, although product formation observed large extent. Alkynes react with chemoselectivity versus alkenes. contrast FeO/MgO, Pt carbon efficiently diboronation silaboration alkynes at lower temperature render cis configured diboronated silaborated alkene.

参考文章(43)
P. H. Hermans, Über die Konstitution der Borsäuren und einiger ihrer Derivate Zeitschrift für anorganische und allgemeine Chemie. ,vol. 142, pp. 83- 110 ,(1925) , 10.1002/ZAAC.19251420107
Arkaitz Correa, Carsten Bolm, Iron-Catalyzed CN Cross-Coupling of Sulfoximines with Aryl Iodides Advanced Synthesis & Catalysis. ,vol. 350, pp. 391- 394 ,(2008) , 10.1002/ADSC.200700508
Irina Beletskaya, Christina Moberg, Element-element additions to unsaturated carbon-carbon bonds catalyzed by transition metal complexes. Chemical Reviews. ,vol. 106, pp. 2320- 2354 ,(2006) , 10.1021/CR050530J
Avelino Corma, Hermenegildo Garcia, Supported gold nanoparticles as catalysts for organic reactions Chemical Society Reviews. ,vol. 37, pp. 2096- 2126 ,(2008) , 10.1039/B707314N
Toshimichi Ohmura, Kazuyuki Oshima, Hiroki Taniguchi, Michinori Suginome, Switch of Regioselectivity in Palladium-Catalyzed Silaboration of Terminal Alkynes by Ligand-Dependent Control of Reductive Elimination Journal of the American Chemical Society. ,vol. 132, pp. 12194- 12196 ,(2010) , 10.1021/JA105096R
Tatsuo Ishiyama, Nobuo Matsuda, Norio Miyaura, Akira Suzuki, Platinum(0)-catalyzed diboration of alkynes Journal of the American Chemical Society. ,vol. 115, pp. 11018- 11019 ,(1993) , 10.1021/JA00076A081
Michael Haberberger, Elisabeth Irran, Stephan Enthaler, Synthesis, Characterization and Catalytic Application of Iron Complexes Modified by Monodentate Phosphane Ligands European Journal of Inorganic Chemistry. ,vol. 2011, pp. 2797- 2802 ,(2011) , 10.1002/EJIC.201100233
Toshimichi Ohmura, Michinori Suginome, Silylboranes as New Tools in Organic Synthesis Bulletin of the Chemical Society of Japan. ,vol. 82, pp. 29- 49 ,(2009) , 10.1246/BCSJ.82.29