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Catalytic Enantioselective Reaction

Research Project

Project/Area Number 01470137
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionUniversity of Tokyo

Principal Investigator

KOBAYASHI Susumu (1991)  Fac. of Pharm. Sciences, Assoc. Prof, 薬学部, 助教授 (70101102)

大野 雅二 (1989-1990)  東京大学, 薬学部, 教授 (00111550)

Co-Investigator(Kenkyū-buntansha) 小林 進  東京大学, 薬学部, 助教授 (70101102)
Project Period (FY) 1989 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1991: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1990: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1989: ¥2,800,000 (Direct Cost: ¥2,800,000)
Keywordscatalytic reaction / enantioselective reaction / alkylation / sulfonamide / dialkylzinc / cyclopropanation / chiral Lewis acid / 触媒的不斉反応 / ジエチル亜鉛 / ジヨ-ドメタン / アリルアルコ-ル / 触媒反応 / 不斉アルキル化 / 不斉シクロプロパン化 / カルベノイド / 不斉アルキル化反応 / オルトチタネ-ト
Research Abstract

An enantioselective rraction ffimugh a catalytic process is now recognized as one of the most important and challenging problems in organic synthesis. There have been reported a number of chiml Lewis acids modified by a variety of chiral ligands such as chiml alcohols or amities. However, such an electron-donating ligand decreases the acidity of the Lewis acid. In order to realize efficient catalytic process, we reasoned that the rate accelomting effect or attractive effect of the catalyst seemed to be important in addition to the sterwwntrol and the facile exchange of the product with the substrate on the catalyst. Based on this consideration we became interested in modifying a Lewis acid by electron-withdrawing chiral ligands rather than chiral alcohols or amities. In such a modified Lewis acid, the chiral ligand will not only provide a chiral environment but also increase the acidity of the Lewis acid. Among various acidic compounds we selected C_2-symmetric sulfonamide as a chiral ligand. We have developed two types of catalytic enantioselective reactions. (1) Alkylation of an aldehyde with dialkylzinc, Ti(O-i-Pr)_4 and disulfonamide, and (2) Cyclopropanation of an allylic alcohol using CH_2I_2, Et_2Zn and disulfonamide. Significant features of alkylation are unprecedent high catalytic turnover (up to 2, 000 times) as well as excellent enantioselectivity. The present cyclopropanation is the first example of a catalytic and enantioselective cyclopropanation. And these results will strongly demonstrate that the concept of modifying a Lewis acid with chiral sulfonmft ligand is promising in developing other types of catalytic enantioselective reactions.

Report

(4 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • 1989 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] M.Yoshioka: "Asymmetric Induction CatalyZed by Conjugate Base of Chiral Proton Acids as Ligands:Enantioselective Addition of Dialkylzinc-Outhctitanate Complex to BenZaldehyde with Catalytic Ability of a Remarkable High Order." Tetrahedron Letters.30. 1657-1660 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Takahashi: "Enantioselective Alkylation of Aldehyde CatalyZed by Disulfonamide-Ti(OiPr)_4-Dialkyl Zinc System." Tetrahedron Letters.30. 7095-7098 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Takahashi: "A Catalytic Enantioselective Reaction Using A C_2-Symmetric Disulfonamide as a Chiral Ligand:Cyclopropanation of Allylic Alcohols by the Et_2Zn-CH_2l_2-Disulfonamide System," Tetrahedron Letters.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Takahashi: "A Catalytic.Enamtioselective Reaction Using a C_2-Symmetric Disulfonamide as a Chiral Ligand:Alkylation of Aldehyde CatalyZed by the Disulfonamide-TiloiPrl_4-Dialkylzinc System." Tetrahedron.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshioka, T. Kawakita, and M. Ohno: "Asymmetric Induction Catalyzed by Conjugate Base of Chiral Proton Acids as Ligands ; Enantioselective Addition of Dialkylzinc-Orthotitanate Complex to Benzaldehyde with Catalytic Ability of a Remarkable High Order." Tetrahedron Lett. 30. 1657-1660 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Takahashi, T. Kawakita, M. Yoshioka, S. Kobayashi, and M. Ohno: "Enantioselective Alkylation of Aldehyde Catalyzed by Disulfonamide-Ti(O-i-Pr)_4-Dialkyl Zinc System." Tetrahedron Lett.30. 7095-7098 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Takahashi, M. Yoshioka, M. Ohno, and S. Kobayashi: "A Catalytic Enantioselective Reaction Using a C_2-Symmetric Disulfonamide as a Chiral Ligand : Cyclopropanation of Allylic Alcohols by the Et_2Zn-CH_2I_2-Disulfonamide System." Tetrahedron Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Takahashi, T. Kawakita, M. Ohno, M. Yoshioka, and S. Kobayashi: "A Catalytic Enantioselective Reaction Using a C_2-Symmetric Disulfonamide as a Chiral Ligand : Alkylation of Aldehyde Catalyzed by the Disulfonamide-Ti(O-i-Pr)_4-Dialkyl Zinc System." Tetrahedron.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 高橋 秀依: "A Catalytic Enantioselective Reaction Using a C_2ーSymmetric Disulfonamide as a Chiral Ligand:Cyclopropanation of Allylic Alcohols by the ET_2ZnーCH_2I_2ーDisulfonamide System" Tetrahedron Letters.

    • Related Report
      1991 Annual Research Report
  • [Publications] 高橋 秀依: "A Catalytic Enantioselective Reaction Using a C_2ーSymmetric Disulfonamide as a Chiral Ligand :Alkylation of Aldehyde Catalyzed by DisulfonamideーTi(OーiーPr)_4ーDialtyl Zinc System" Tetrahedron.

    • Related Report
      1991 Annual Research Report
  • [Publications] 高橋 秀依,川北 隆,吉岡 正人,小林 進,大野 雅二: "Enantioselective Alkylation of Aldehyde Catalyzed by DisulfonamideーTi(OーiーPr)_4ーDialkyl Zinc System" Tetrahedron Letters. 30. 7095-7098 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] 高橋 秀依,吉岡 正人,小林 進,大野 雅二: "Enantioselective Cyclopropanation of Allyl Alcohols Catalyzed by DisulfonamideーEt_2ZnーCH_2I_2 System"

    • Related Report
      1990 Annual Research Report
  • [Publications] Hideyo Takahashi 高橋秀依: "Enantioselective Alkylation of Aldehyde Catalyzed by Disulfonamide-Ti(O-i-Pr)_4-Dialkyl Zinc System" Tetrahedron Letters. 30. 7095-7098 (1989)

    • Related Report
      1989 Annual Research Report

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

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