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Catalytic Hydroboration Reaction and Synthetic Application

Research Project

Project/Area Number 01550660
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionHokkaido University

Principal Investigator

MIYAURA Norio  Hokkaido Univ,. Fac,. of Eng., Associate Pro,., 工学部, 助教授 (10002049)

Co-Investigator(Kenkyū-buntansha) HARA Syoji  Hokkaido Univ,. Fac,. of Eng,. Research Asso,., 工学部, 助手 (20109490)
Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1990: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1989: ¥1,200,000 (Direct Cost: ¥1,200,000)
KeywordsHydroboration / Catecholborane / Rhodium-catalyst / Palladium-catalyst / Allylic boronate / Asymmetric hydroboration / Rhー触媒 / Pdー触媒 / ロジウム触媒反応 / テトラキス(トリフェニルホスフィン)パラジウム(0) / クロスカラプリング
Research Abstract

Recently, Noth and Manning reported that alkenes and alkynes can be hydroborated with catecholborane in the presence of Rh-catalyst under extremely mild conditions. Although catalytic hydrometalations such as hydrosilylation were widely examined, only a few reports were published on the catalytic hydroboration, because the reaction with most of hydroborating reagents proceeds readily without any catalysts. We applied the catalytic method for the following synthetic reactions.
The hydroboration of alkenes can tolerate various functionalities such as cyano and alkoxycarbonyl groups, however, more reactive keto group must be protected. On the other hand, the catalytic hydroboration of allyl acetone with catecholborane in the presence of 1 mole% of RhCl(PPh_3)_3 at 0 ^゚C proceeds chemoselectively at the carbon-carbon double bond but not at the keto group. The boronyl ketones thus obtained were subjected to coupling with aryl and 1-alkenyl halides to give corresponding ketones in 62-69% yiel … More ds. The coupling reaction was successfully induced by thallium (I) carbonate in the presence of palladium catalyst.
Although the hydroboration approach is simple and convenient, the method is not applicable to usual 1, 3-dienes because the hydroboration mainly occurs at the terminal double bond to give homoallylic boranes. We found that a catalytic 1, 4-hydroboration of 1, 3-dienes with catecholborane in the presence of Pd (PPh_3)_4 or Rh_4(CO)_<12> to afford (Z)-allylic boronates with high isomeric purity, over 99%.
Several rhodium (I) complexes containing chiral phosphine, (+) DIOP, (+) BINAP, (S, S) CHIRAPHOS, and (S) (R) BPPFA, have been found to be effective as catalyst for the asymmetric hydroboration of prochiral alkenes with catecholborane (1, 3, 2-benzodioxaborole) to give optically active 2-alkyl-1, 3,2-benzodioxaboroles. Among the ligands examined, DIOP has been recognized to be most effective to give high asymmetric inducation. We obtained a 74% ee for the hydroboration of indene. Less

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] M.Sato,N.Miyaura,and A.Suzuki: "CrossーCoupling Reaction of Alkylーor Arylboronic Acid Esters with Organic Halides田Induced by Thallium(I) Salts and PalladiumーCatalyst." Chem.Lett.1405-1408 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M.Sato.N.Miyaura,and A.Suzuki: "New Convenient Approach to the Preparation of (Z)ーAllylic Boronates via Catalytic.1,4ーHydroboration of 1,3ーDienes with Catecholborane." Tetraheron Lett.30. 3789-3792 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M.Sato,N.Miyaura,and A.Suzuki: "Rhodium(I)ーCatalyzed Asymmetric Hydroboration of Alkenes with 1,3,2ーBenzodioxaborole." Tetrahedron Lett.31. 231-234 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T.Ohーe,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzed CrossーCoupling Reaction of Aryl or Vinylic Triflates with Organoboron Compounds." Synlett.221-223 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M. Sato, N. Miyaura, and A. Suzuki: "Cross-Coupling Reaction of Alkyl- or Arylboronic Acid Esters with Organic Halides Induced by Thallium (I) Salts and Palladium-Catalyst." Chem. Lett.1405-1408 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M. Sato, Y. Nomoto, N。 Miyara, and A. Suzuki: "New Convenient Approach to the Preparation of (Z)-Allylic Boronates via Catalytic 1, 4-Hydroboration of 1, 3-Dienes with Catecholborane." Tetrahedron Lett.30. 3789-3792 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M. Sato, N. Miyaura, and A. Suzuki: "Rhodium-Catalyzed Asymmetric Hydroboration of Alkenes with 1, 3, 2-Benzodioxaborole." Tetrahedron Lett.31. 231-234 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. OH-e, N. MIYAURA, and A. SUZUKI: "Palladium-Catalyzed Cross-Coupling Reaction of Aryl or Vinylic Triflates with Organoboron Compounds." Synlett.221-223 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M.Sato,N.Miyaura,and A.Suzuki: "Rhodium(I)ーCatalyzed Asymmetric Hydroboration of Alkenes with 1,3,2ーBenzodioxaborole." Tetrahedron Letter. 31. 321-234 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Ohe,N。Miyaura,and A.Suzuki: "PalladiumーCatalyzed CrossーCoupling Reaction of Aryl or Vinylic Triflates with Organoboron Compounds." Synlett.221-223 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Sato: "Cross-Couping Reaction of Alkyl- or Arylboronic Esters with Organic Halides Induced by Thallium(I)Salts and Palladium-Catalyst" Chemistry Letter. 1405-1408 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Sato: "New Convenient Approach to the Preparation of(Z)-Allylic Boronates via Catalytic 1,4-Hydroboration of 1,3-Dienes with Catecholborane" Tetrahedron Letter. 30. 3789-3792 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Yanagi: "Stereoselective Synthesis of Conjugated 2,4-Alkadienoates via the Palladium-Catalyzed Cross-Coupling Reaction of 1-Alkenylboronates" Bull.Chem.Soc.Jpn.62. 3892-3896 (1989)

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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