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2005 Fiscal Year Final Research Report Summary

Developments of Direct Synthesis and New Catalytic Reactions of Aromatic Boron Compounds

Research Project

Project/Area Number 16550089
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionHOKKAIDO UNIVERSITY

Principal Investigator

ISHIYAMA Tatsuo  Hokkaido Univ., Grad.School of Eng., Asso.Prof., 大学院・工学研究科, 助教授 (00232348)

Co-Investigator(Kenkyū-buntansha) YAMAMOTO Yasunori  Hokkaido Univ., Grad.School of Eng., Inst., 大学院・工学研究科, 助手 (30271646)
Project Period (FY) 2004 – 2005
KeywordsAromatic Boron Compound / Activation of Aromatic C-H Bond / Borylation / Iridium Catalyst / Palladium Catalyst / Unsymmetrical Biaryl / β-Arylketone
Research Abstract

1.Iridium-Catalyzed Aromatic C-H Borylation
Aromatic C-H borylation of arenes and heteroarenes using stoichiometric amounts of bis(pinacolate)diboron or pinacolborane was catalyzed by an iridium complex generated from 1/2[Ir(OMe)(COD)]_2 and 4,4'-di-tert-butyl-2,2'-bipyridine at room temperature in hexane and afforded the corresponding aromatic and heteroaromatic boron compounds in high yields with excellent regioselectivities. The reactions tolerated various functionalities such as halogen, carbonyl, and cyano groups or benzylic C-H bonds. A reaction mechanism may involve generation of a tris(boryl)iridium(III) complex by the reaction of an iridium(I) complex with bis(pinacolato)diboron or pinacolborane, oxidative addition of an aromatic C-H bond to the tris(boryl)iridium(III) complex, and reductive elimination of an aromatic boron compound. Sequential reactions, involving iridium-catalyzed aromatic C-H borylation and palladium-catalyzed cross-coupling with aromatic halides, provided a … More one-pot procedure for the synthesis of various unsymmetrical biaryls.
2.Palladium-Catalyzed 1,4-Addition of Aromatic Boron Compounds to Enones
1,4-Addition of aromatic boron compounds to cyclic and acyclic enones was catalyzed by dicationic palladium(II) complexes such as [Pd(dppe)(PhCN)_2](SbF_6)_2 and nitrile free complexes. A catalytic cycle involving transmetalation between an aromatic boron compound and a dicationic palladium complex to give a cationic arylpalladium(II) intermediate, insertion of an enone into a carbon-palladium bond, giving a palladium enolate, and finally hydrolysis with water to regenetrate the dicationic palladium species was proposed. Asymmetric reactions were carried out in aqueous methanol in the presence of a chiral phosphine-dicationic palladium(II) catalyst. A palladium complex of (S,S)-dipamp gave optically active β-arylketones up to 96% ee for 2-cyclohexenone and 2-cycloheptenone. A palladium-(S,S)-chiraphos complex resulted in 82-97% ee for 2-cyclopentenone and acyclic ketones. Less

  • Research Products

    (34 results)

All 2006 2005 2004 2003

All Journal Article (30 results) Book (3 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Fluorescence properties of the chlorophyll d-dominated cyanobacterium Acaryochloris sp. strain Awaji,2006

    • Author(s)
      S.Akimoto, A.Murakami, M.Yokono, K.Koyama, T.Tsuchiya, H.Miyashita, I.Yamazaki, M.Mimuro
    • Journal Title

      J. Photochem. Photobiol. A : Chemistry 178

      Pages: 122-129

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Luminescent properties of CdS nanoclusters dispersed in solution-Effects of size and surface termination2006

    • Author(s)
      M.Okamura, K.Ebina, S.Akimoto, I.Yamazaki, K.Uosaki
    • Journal Title

      J. Photochem. Photobiol. A : Chemistry 178

      Pages: 156-161

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Solvent-assisted intramolecular vibrational energy redistribution of S_1 perylene in ketone solvents2006

    • Author(s)
      T.Kiba, S.Sato, S.Akimoto, T.Kasajima, I.Yamazaki
    • Journal Title

      J. Photochem. Photobiol. A : Chemistry 178

      Pages: 201-207

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Transition Metal-Catalyzed Direct Borylation and Silylation Based on C-H Activation2005

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      J. Synth. Org. Chem., Jpn. 63・5

      Pages: 440-452

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Regioselective Aromatic C-H Silylation of Five-Membered Heteroarenes with Fluorodisilanes Catalyzed by Iridium(I) Complexes2005

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Chem. Commun. -・40

      Pages: 5065-5067

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Mechanism of the Mild Functionalization of Arenes by Diboron Reagents Catalyzed by Iridium Complexes. Intermediacy and Chemistry of Bipyridine-Ligated Iridium Trisboryl Complexes2005

    • Author(s)
      Timothy M.Boller
    • Journal Title

      J. Am. Chem. Soc. 127・41

      Pages: 14263-14278

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Iridium-Catalyzed C-H Borylation of Arenes and Heteroarenes : 1-Chloro-3-iodo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene and 2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)indole2005

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Org. Synth. 82・-

      Pages: 126-133

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Asymmetric 1,4-Addition of Potassium Aryltrifluoroborates [ArBF_3]K to Enones Catalyzed by Dicationic Palladium(II) Complexes2005

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Chem. Lett. 34・5

      Pages: 720-721

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Chiral Bis-phosphoramidites Based on Linked-BINOL for Rhodium-Catalyzed 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Carbonyl Compounds2005

    • Author(s)
      Yasunori Yamamoto
    • Journal Title

      Chem. Lett. 34・9

      Pages: 1224-1225

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Enantioselective 1,4-Addition of Ar_3Bi, [ArBF_3]K, and ArSiF_3 to Enones Catalyzed by a Dicationic Palladium(II)-Chiraphos or -Dipamp Complex2005

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Organometallics 24・21

      Pages: 5025-5032

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Excitation energy transfer in the antenna system with divinyl-chlorophylls in the vinyl reductase-expressing Arabidopsis2005

    • Author(s)
      S.Akimoto, M.Yokono, M.Ohmae, I.Yamazaki, N.Nagata, R.Tanaka, A.Tanaka, M.Mimuro
    • Journal Title

      Chem. Phys. Lett. 409

      Pages: 167-171

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Ultrafast excitation relaxation dynamics of lutein in solution and in the light-harvesting complexes II isolated from Arabidopsis thaliana2005

    • Author(s)
      S.Akimoto, M.Yokono, M.Ohmae, I.Yamazaki, A.Tanaka, M.Higuchi, T.Tsuchiya, H.Miyashita, M.Mimuro
    • Journal Title

      J. Phys. Chem. B 109

      Pages: 12612-12619

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Transition Metal-Catalyzed Direct Borylation and Silylation Based on C-H Activation2005

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      J.Synth.Org.Chem., Jpn. 63-5

      Pages: 440-452

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Regioselective Aromatic C-H Silylation of Five-Membered Heteroarenes with Fluorodisilanes Catalyzed by Iridium(I) Complexes2005

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Chem.Commun. 40

      Pages: 5065-5067

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Mechanism of the Mild Functionalization of Arenes by Diboron Reagents Catalyzed by Iridium Complexes. Intermediacy and Chemistry of Bipyridine-Ligated Iridium Trisboryl Complexes2005

    • Author(s)
      Timothy M.Boller
    • Journal Title

      J.Am.Chem.Soc. 127-41

      Pages: 14263-14278

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Iridium-Catalyzed C-H Borylation of Arenes and Heteroarenes : 1-Chloro-3-iodo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene and 2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)indole2005

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Org.Synth. 82

      Pages: 126-133

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric 1,4-Addition of Potassium Aryltrifluoroborates [ArBF_3]K to Enones Catalyzed by Dicationic Palladium(II) Complexes2005

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Chem.Lett. 34-5

      Pages: 720-721

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Chiral Bis-phosphoramidites Based on Linked-BINOL for Rhodium-Catalyzed 1,4-Addition of Arylboronic Acids to αβ-Unsaturated Carbonyl Compounds2005

    • Author(s)
      Yasunori Yamamoto
    • Journal Title

      Chem.Lett. 34-9

      Pages: 1224-1225

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enantioselective 1,4-Addition of Ar_3Bi, [ArBF_3]K, and ArSiF_3 to Enones Catalyzed by a Dicationic Palladium(II)-Chiraphos or -Dipamp Complex2005

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Organometallics 24-21

      Pages: 5025-5032

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Metal-Catalyzed Reactions of Diborons for Synthesis of Organoboron Compounds2004

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Chem. Rec. 3・5

      Pages: 271-280

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Asymmetric 1,4-Addition of Triarylbismuths to Enones Catalyzed by Dicationic Palladium(II) Complexes2004

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Chem. Commun. -・16

      Pages: 1822-1823

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] 1,4-Addition of Arylboronic Acids and Arylsiloxanes to α,β-Unsaturated Carbonyl Compounds via Transmetalation to Dicationic Palladium(II)Complexes2004

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Organometallics 23・18

      Pages: 4317-4324

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Iridium-Catalyzed Hydroboration of Alkenes with Pinacolborane2004

    • Author(s)
      Yasunori Yamamoto
    • Journal Title

      Tetrahedron 60・47

      Pages: 10695-10700

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Metal-Catalyzed Reactions of Diborons for Synthesis of Organoboron Compounds2004

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Chem.Rec. 3-5

      Pages: 271-280

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric 1,4-Addition of Triarylbismuths to Enones Catalyzed by Dicationic Palladium(II) Complexes2004

    • Author(s)
      Takashi Nishikata
    • Journal Title

      Chem.Commun. 16

      Pages: 1822-1823

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] 1,4-Addition of Arylboronic Acids and Arylsiloxanes to αβ-Unsaturated Carbonyl Compounds via Transmetalation to Dicationic Palladium(II) Complexes2004

    • Author(s)
      Takashhi Nishikata
    • Journal Title

      Organometallics 23-18

      Pages: 4317-4324

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Iridium-Catalyzed Hydroboration of Alkenes with Pinacolborane2004

    • Author(s)
      Yasunori Yamamoto
    • Journal Title

      Tetrahedron 60-47

      Pages: 10695-10700

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Formation of Carbon-Boron Bonds by Cross-Coupling Reactions2004

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      103 Catalysis for Organic Syntheses

      Pages: 144-145

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cross-Coupling Reactions2004

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      The Firth Series of Experimental Chemistry, Vol.18 Synthesis of Organic Compounds Vol.18

      Pages: 327-352

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] One-Pot Synthesis of Unsymmetrical 1,3-Dienes through Palladium-Catalysed Sequential Borylation of a Vinyl Electrophile by a Diboron and Cross-Coupling with a Distinct Vinyl Electrophile2004

    • Author(s)
      Tatsuo Ishiyama
    • Journal Title

      Catalysts for Fine Chemical Synthesis 3

      Pages: 70-74

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] Excitation relaxation dynamics of carotenoids probed by ultrafast fluorescence spectroscopy, in N. Wada and M. Mimuro (Eds.), Bio/Chemiluminescence and its application to photosynthesis2005

    • Author(s)
      S.Akimoto, M.Mimuro
    • Total Pages
      22(213-234)
    • Publisher
      Research Signpost, Kerala, India
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] 有機合成のための触媒反応1032004

    • Author(s)
      石山竜生
    • Total Pages
      215
    • Publisher
      東京化学同人
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] 第5版 実験化学講座 18巻 有機化合物の合成VI 金属を用いる有機合成2004

    • Author(s)
      石山竜生
    • Total Pages
      470
    • Publisher
      丸善
    • Description
      「研究成果報告書概要(和文)」より
  • [Patent(Industrial Property Rights)] オルガノシラン類の製造方法2003

    • Inventor(s)
      宮浦憲夫
    • Industrial Property Rights Holder
      東レ・ダウコーニング ・シリコーン株式会社
    • Industrial Property Number
      JP 2005075807 A2 20050324
    • Filing Date
      2003-09-03
    • Acquisition Date
      2005-03-24
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2007-12-13  

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