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含ホウ素環状化合物の合成を指向した効率的ホウ素化反応の開発

Research Project

Project/Area Number 14044004
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionHokkaido University

Principal Investigator

宮浦 憲夫  北海道大学, 大学院・工学研究科, 教授 (10002049)

Co-Investigator(Kenkyū-buntansha) 山本 靖典  北海道大学, 大学院・工学研究科, 助手 (30271646)
石山 竜生  北海道大学, 大学院・工学研究科, 助教授 (00232348)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥4,500,000 (Direct Cost: ¥4,500,000)
Fiscal Year 2003: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 2002: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywords環状有機ホウ素化合物 / クロスカップリング反応 / イリジウム触媒 / ニッケル触媒 / ジボロン / 直接ホウ素化反応 / 分子内アリルホウ素化反応 / 触媒的異性化反応
Research Abstract

芳香族C-H結合活性化
芳香族C-H結合の活性化において反応条件を精査した結果、配位子に4,4'-di(t-butyl)-2,2'-bipyridineを用いると触媒はさらに高活性を示し、量論量の芳香族化合物を室温で直接ホウ素化できるようになった。また、反応の機構的調査よりホウ素源としてピナコールボランも利用可能となった。さらに、ジシランを用いた直接ケイ素化にも成功した。含ヘテロ芳香族化合物の直接ホウ素化も可能になり、ヘテロアリールホウ酸エステルが簡便に合成できるようなった。
触媒的異性化反応を利用した短段階 γ(ω-formylalkoxy)allylboraneの合成と環化反応
触媒的二重結合異性化反応は、異性化後の二重結合の立体制御が困難でこれまで有機合成に利用された例は少ないが、γアルコキシビニルホウ素化合物を選択的にγ-アルコキシアリルホウ素化合物へ変換できることをすでに見いだしている。イリジウム触媒を用いるとトランス選択的に異性化する。また、ニッケル触媒を用いるとシス選択的に異性化することが分かった。本年度は、8員環-環状エーテルを、イリジウム触媒を用いた異性化反応からトランス-8員環エーテル、ニッケル触媒を用いた異性化からジス-8員環エーテルを立体選択的に合成した。

Report

(2 results)
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] T.Ishiyama: "Direct synthesis of aryl halosilanes through iridium(I)-catalyzed aromatic C-H silylation by disilanes."Angewandte Chemie, International Edition. 42・43. 5346-5348 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ishiyama: "Palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron with vinyl triflates β-substituted by a carbonyl group : efficient synthesis of β-boryl-α,β-unsaturated carbonyl compounds and their synthetic utility."Journal of Organometallic Chemistry. 687・2. 284-290 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ishiyama: "Room temperature borylation of arenes and heteroarenes using stoichiometric amounts of pinacolborane catalyzed by iridium complexes in an inert solvent."Chemical Communications. 23. 2924-2925 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ishiyama: "Iridium-catalyzed direct borylation of five-membered heteroarenes by bis(pinacolato)diboron : Regioselective, stoichiometric, and room temperature reactions."Advanced Synthesis & Catalysis. 345・9-10. 1103-1106 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ishiyama: "Transition metal-catalyzed borylation of alkanes and arenes via C-H activation."Journal of Organometallic Chemistry. 680・1-2. 3-11 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Yamamoto: "Intramolecular allylboration of γ-(ω-formylalkoxy)allylboronates for syntheses of trans- or cis-2-(ethenyl)tetrahydropyran-3-ol and 2-(ethenyl)oxepan-3-ol."Tetrahedron. 59・4. 537-542 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yamamoto, Y., Kurihara, K., Yamada, A., Takahashi, M., Takahashi, Y., Miyaura, N.: "Intramolecular allylboration of γ-(ω-formylalkoxy)allylboronates for syntheses of trans-or cis-2-(ethenyl)tetrahydropyran-3-ol and 2-(ethenyl)oxepan-3-ol"Tetrahedron. 59. 537-542 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Ishiyama Tatsuo, Oohashi Zengo, Ahiko Taka-Aki, Miyaura Norio: "Nucleophilic borylation of benzyl halides with bis(pinacolato)diboron catalyzed by pulladium(0) complexes"Chemistry Letters. 65(14). 780-781 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takagi Jun, Takahashi Kou, Ishiyamu Tatsuo, Miyaura Norio: "Palladium-Catalyzed Cross-Coupling Reaction of Bis(pinacolato)diboron with 1-Alkenyl Halides or Triflates : Convenient Synthesis of Unsymmetrical 1,3-Dienes via the Borylation-Coupling Sequence"Journal of the American Chemical Society. 124. 8001-8006 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takagi Jun, Kamon Akihiro, Ishiyama Tatsuo, Miyaura Norio: "Synthesis of β-boryl-α, β-unsaturated carbonyl compounds via palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron with vinyl triflates"Synlett. 1880-1882 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Ishiyama, J.Takagi, K.Ishida, N.Miyaura, N.R.Anastasi, J.F.Hartwig: "Mild Iridium-Catlyzed Borylation of Arenes. High Turnover Numbers, Room Tempreture Reaction, and Isolation of a Potential Intermediate"Journal of the American Chemical Society. 124. 390-391 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takagi Jun, Sato Kazuaki, Hartwig John F., Ishiyama Tatsuo, Miyaura Norio: "Iridium-catalyzed C-H coupling reaction of heteroaromatic compounds with bis(pinacolato)diboron : regioselective synthesis of heteroarylboronates"Tetrahedron Letters. 43. 5649-5651 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Ishiyama Tatsuo, Takagi Jun, Hartwig John F., Miyaura Norio: "A stoichiometric aromatic C-H borylation catalyzed by iridium(I)/2, 2'-bipyridine complexes at room temperature"Angewandte Chemie, International Edition. 41. 3056-3058 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2018-03-28  

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