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Exploitation of Practical Method for Asymmetric Functionalization of Alkenes

Research Project

Project/Area Number 09554048
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 物質変換
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

KATSUKI Tsutomu  Kyushu Univ., Fac. Sci., Professor, 大学院・理学研究科, 教授 (40037271)

Co-Investigator(Kenkyū-buntansha) SUZUKI Kenji  Nissan Chem. Ind. Ltd., Res. Chairman, 中央研究所, 主任研究員
IRIE Ryo  Kyushu Univ., Fac. Sci., Research Associate, 大学院・理学研究科, 助手 (70243889)
ITO Yoshio  Kyushu Univ., Fac. Sci., Associate Professor, 大学院・理学研究科, 助教授 (00221086)
鈴木 健二  日産化学工業株式会社, 中央研究所, 主任研究員
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥12,100,000 (Direct Cost: ¥12,100,000)
Fiscal Year 1999: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1998: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1997: ¥7,100,000 (Direct Cost: ¥7,100,000)
Keywords(salen)manganese / asymmetric epoxidation / cyclopropanation / desymmetrization / (salen)ruthenium / pyridine N-oxide / (salen)cobalt(II) / tris(oxazoline)copper / 不斉シクロプロパン化 / 高シス選択的 / 高エナンチオ選択的 / サレンバルト錯体 / ヘテロディールスアルダー / 不斉ヒドロキシル化反応 / サレン-マンガン錯体 / 光学活性ラクタム / 不斉Kharash-Sosnovsky反応 / 不斉アリル位酸化 / トリスオキサゾリン-銅錯体 / 過酸エステル / 過カルバミン酸エステル / アリル位アミノ化 / 不斉ベンジル位アミノ化
Research Abstract

We have studied asymmetric epoxidation using optically active (salen)manganese complexes and applied for the synthesis of several optically active important compounds. In this research project, we aimed at extension of the scope of substrates used in the epoxidation and exploitation of new chiral complexes to enable several important asymmetric reactions such as asymmetric oxidation of C-H bond, cis-selective asymmetric cyclopropanation. During three years, we could receive following impressive results.
1. Enantioselective hydroxylation of C-H bond of meso-tetrahydrofurans was found to proceed with high selectivity (up to 90% ee) by using optically active (salen)manganese complex as a catalyst. This asymmetric reaction was successfully applied to the synthesis of (-)- Alloyohimbane and (-)-Swainsonine.
2. Newly prepared (salen)ruthenium complex bearing nitrosyl group at the apical position was found to show unique asymmetric catalysis. Under the irradiation, the complex showed catalytic activity for epoxidation by using 2, 6-dichloropyridine N-oxide as a terminal oxidant. High enantioselectivity was observed not only for the epoxidation of cis-disubstituted olefins but also that of trans- and terminal olefins differing from the previously reported epoxidation catalyzed by (salan)manganese complex. Furthermore, the reaction was highly stereospecific and produced epoxides without isomerization of the geometry of double bond.
3. Highly cis- and enantio-selective cyclopropanation was realized by using (salen)cobalt(II) complex. By this achievement, all the possible stereochemistry in cyclopropanation could be for the first time controlled chemically.
4. High enantioselectivity more than 80% ee could be observed in the asymmetric C-H Oxidation at a allylic position of racemic olefins by using optically active tris(oxazoline)copper complex.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] A. Miyafuji: "Enantiotopic Place-Selective C-H Oxidation Using (Salen) manganese (III) Complex as a Catalyst."Synlett. ・7. 863-838 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Fukada: "Highly Enantioselective Cyclopropanation of Styrene Derivatives Using Co(III)-Salen Complex as a Catalyst."Tetrahedron. 53・21. 7201-7208 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kohmura Benzylic and Allylic Amination.: Synlett. ・12. 1456-1458 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Miyafuji: "Asymmetric Desymmetrization of meso-Tetrahydrofuran Derivatives by Highly Enantiotopic Selective C-H Oxidation"Tetrahedron. 54・35. 10339-10348 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Uchida: "Ru-Salen Catalyzed Asymmetric Epoxidation: Photoactivation of Catalytic Activity."Synlett. ・7. 1157-1159 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kohmura: "Oxidative Asymmetrization of Racemic Alkenes: Asymmetric Synthesis of Optical Active Dicyclopentadiene Derivatives."Synlett. ・8. 1231-1234 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Fukuda: "Catalytic Asymmetric [2,3] Sigmatropic Rearrangement: Co(III)-Salen Catalyzed S-Ylide Formation from Allyl Aryl Sulfides and Their Rearrangement."Tetrahedron. 55・. 649-664 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Miyafuji: "Application of Oxidative Desymmetrization of meso-Tetrahydrofurans: Synthesis of Functionalized Chiral Building Blocks and of (-)-Alloyohimbane."Heterocycles. 52・1. 261-272 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Niimi: "Co-Salen Catalyzed Highly cis- and Enantio-selective Cyclopropanation."Tetrahedron Lett. (印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Punniyamurthy: "Ashort Step Enantioselective Synthesis of (-)-Swainsonine."Chirality. (印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Miyafuji and T. Katsuki: "Enantiotopic Place-Selective C-H oxidation Using (Salen)manganese(III) Complex as a Catalyst"Synlett.. 1997(7). 836-838 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Fukuda and T. Katsuki: "Highly Enantioselective Cyclopropanation of Styrene Derivatives Using Co(III9-Salen Complex as a Catalyst"Tetrahedron. 53(21). 7201-7208 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kohmura, K. Kawasaki, and T. Katsuki: "Benzylic and Allylic Amination"Synlett.. 1997(12). 1456-1458 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Miyafuji and T. Katsuki: "Asymmetric Desymmetrization of meso- Tetrahydrofuran Derivatives by Highly Enantiotopic Selective C-H Oxidation"Tetrahedron. 54(35). 10339-10348 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Takeda, R. Irei, Y. Shinoda, and T. Katsuki: "Ru-Salen Catalyzed Asymmetric Epoxidation : Photoactivation of Catalytic Activity"Synlett.. 19997). 1157-1159 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kohmura and T. Katsuki: "Oxidative Asymmetrization of Racemic Alkenes : Asymmetric Synthesis of Optically Active Dicyclopentadiene Derivatives"Synlett.. 1999(8). 1231-1234 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Fukuda, R. Irei, and T. Katsuki: "Catalytic Asymmetric [2, 3] Sigmatropic Rearrangement : Co(III9-Salen Catalyzed S-Ylide Formation from Allyl Aryl Sulfides and Their Rearrangement"Tetrahedron. 55. 649-664 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Miyafuji, K. Ito, and T. Katsuki: "Application of Oxidative Desymmetrization of meso- Tetrahydrofurans : Synthesis of Functionalized Chiral Building Blocks and of(-)-Alloyohimbane"Heterocycles.. 52(1). 261-272 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Niimi, T. Uchida, R. Irie, and T. Katsuki: "Co-Salen Catalyzed Highly cis- and Enantio-selective Cyclopropanation"Tetrahedron Lett.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Punniyamurthy, R, Irie, and T. Katsuki: "A Snort Step Enantioselective Syntheses of (-)-Swainsonine"Chirality. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Punniyamurthy: "A Short Step Enanioselective Synthesis of(-)-Swainsonine"Chirality. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Tatsuo Niimi: "Co-Salen Catalyzed Higyly cis-and Enantio-selective Cyclopropanation"Tetrahedron Letters. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yoshinori Koumura: "Oxidative Asymmetrization of Racemic Alkenes:Asymmetric Synthesis of Optically Active Dicyclopentadiene Derivatives."Synlett. 1999・8. 1231-1234 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Tsutomu Katsuki: "Comprehensive Asymmetric Catalysis, Vol.2"Springer. pp.621-648 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akio Miyafuji: "Asymmetric Desymmetrization of meso-Tetrahydrofuran Derivatives by Highly Enantiotopic Selective C-H Oxidation" Tetrahedron. 54. 10339- (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Punniyamurthy: "Chiral Mn-Salen Catalysed Enantiotopic Selective C-H Oxidation of meso-Pyrrolidine Derivatives." Tetrahedron Letters. 39. 8295- (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Kawasaki: "Enantioselective Allylic Oxidation of Cycloalkenes by Using Cu(II)-Tris(oxazoline)Complex as a Catalyst" Tetrahedron. 53(18). 6337-6350 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Kohmura: "Benzylic and Allylic Amination" Synlett. 12. 1456-1458 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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