• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of Asymmetric Catalysis of Synthetic Reactions

Research Project

Project/Area Number 02403020
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

NAKAI Takeshi  Tokyo Inst. Tech.,Fac. Eng.,Prof., 工学部, 教授 (90016717)

Co-Investigator(Kenkyū-buntansha) TERADA Masahiro  same as above Res.Assoc., 工学部, 助手 (50217428)
TOMOOKA Katsuhiko  same as above Res.Assoc., 工学部, 助手 (70207629)
MIKAMI Koichi  same as above Assoc. Prof., 工学部, 助教授 (10157448)
Project Period (FY) 1990 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥32,500,000 (Direct Cost: ¥32,500,000)
Fiscal Year 1992: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1990: ¥27,500,000 (Direct Cost: ¥27,500,000)
KeywordsAsymmetric Synthesis / Asymmetric Catalysis / Aldol Reaction / Ene Reaction / Diels-Alder Reaction / Titianium Complex / Claisen Rearrangement / Europium Complex / アルド-ル反応 / DielsーAlder反応 / Claisen転位 / ランタニド錯体 / ランタノイド触媒 / 立体制御 / 分子認識
Research Abstract

The purpose of this work is to develop efficient asymmetric catalysis of some C-C bond forming reactions. A summary of the research results is as follow: (1) Catalytic Stereocontrol in Asymmetric Aldol reactions : Using Eu(III)-complexes as a catalyst, high levels of distereocontrol have been achieved in the aldol reactions of chiral alpha-amino aldehydes with ketene silyl acetals Furthermore, the catalytic aldol technology has successfully been applied to asymmetric synthesis of the key intermiediates of carbapenem antibiotics and renin inhibitors. (2) Asymmetric catalysis of Carbonyl-Ene Reactions : The chiral titanium complex derived from optically active binaphthol was found to serve as an efficient asymmetric catalyst for glyoxylate-ene reaction to provide a practical access to alpha-hydroxy esters in high enantiomeric excess. Interestingly, the phenomenon of "asymmetric amplification" was observed and its mechanistic origin was elucidated. (3) Asymmetric Catalysis of Diels-Alder Type Reactions : The above-mentioned chiral titanium comples was found to serve as an asymmetric catalyst for hetero D.-A. reaction with the glyoxylate and D.-A.reactions with methacrolein and quinones. (4) Asymmetric Catalysis of Allylmetal/Aldehyde Addition Reactions : The abovementioned chiral Ti-complex was also found to be an efficient asymmetric catalyst for the addition reactions of allylic silanes and stannanes to the glyoxylate. (5) Asymmetric Catalysis of Claisen Rearrangement : A palladium (II) complex was found to show an efficient and diastereoselective catalysis of the Claisen rearrangement via an ether exchange process. However, the development of an asymmetric catalyst has been still unsuccessful. Further work is in progress.

Report

(4 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • 1990 Annual Research Report
  • Research Products

    (56 results)

All Other

All Publications (56 results)

  • [Publications] Koichi Mikami: "Catalytic Asymmetric Glyoxylate-Ene Reaction:A Practical Access to α-Hydroxy Esters in High Enantiomeric Purities" Journal if American Chemical Society. 112. 3949-3954 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro Terada: "Remarkable Positive Nonlinear Effect in the Enantioselective Glyoxylate-Ene Reaction Catalysed by a Chiral Tiranium Complex" Chrmical Communicarions. 22. 1623-1624 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Carbonyl-Ene Reaction with Vinylsilanes: Silicon As a Controlling Element for the Stereo- and Regiochemisty" Journal of American Chemical Society. 112. 6737-6738 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fimiyuki Shirai: "Diastereofacial Selection in Titanium Tetrachloride-Promoted Aldol Reactions with the Silyl Ketene Acetal of Methyl(R)-3-Hydroxybutanoate" Chemistry Letters. 1931-1934 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 三上 幸一: "カルボニル-エン反応:新しい鎖状立体制御法" 有機合成化学協会誌. 48. 292-303 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 三上 幸一: ""Chemzyme"の創製,不斉触媒的カルボニル-エン反応の開発をケース・スタディーとして" 油化学. 39. 129-137 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro TERADA,Koichi MIKAMI,Takeshi NAKAI: "Enantioselective Hetero-Diels-Alder Reaction with Glyoxylate Catalyzed by Chiral Titanium Complex: Asymmetric Synthesis of the Lactone Portion of Mevinolin and Compactin" Tetrahedron Letters. 32. 935-938 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Takeshi NAKAI: "Unique Catalysis by Eu(dppm)_3:Catalytic Molecular Recognition in Aldol and Michael Reaction" Journal of Organic Chemistry. 56. 5456-5459 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Takeshi NAKAI: "Lanthanide (III) Catalyzed Aldol Reactions of Glyceraldrhyde Acetonide with Ketene Silyl Acetals: Catalytic Asymmetric Route to Monosaccharides" Tetrahedron Asymmetry. 2. 993-996 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Yukihiro MOTOYAMA,Takeshi NAKAI: "Chiral Titanium Complex-Caralyzed Diels-Alder Reaction: A Potential Route to Anthracycline Intermediates" Tetrahedron Asymmetry. 2. 643-646 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Eiji SAWA,Takeshi NAKAI: "Asymmetric Catalysis by Chiral Titanium Perchlorate for Carbonyl-Ene Cycization" Tetrahedron Letter. 32. 6571-6574 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 三上 幸一,寺田 眞浩,成沢 智司,中井 武: "エン反応の不斉触媒化" 化学. 46. 138-139 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro TERADA,Jin-Hua GU,Dibakar C.DEKA,Koichi MIKAMI,Takeshi NAKAI: "Stereo-Modulating Catalysis by Europium(III) Complexes in Aldol Reactions of Chiral α-Alkoxy Aldebydes with Kerene Silyl Acetals" Chemistry Letters. 29-32 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Satoshi MARISAWA,Takeshi NAKAI: "Asymmrtric Catalysis for Car-bonyl-Ene Reaction" Synlett. 255-265 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Jin-Hua GU,Masahiro TERADA,Koichi MIKAMI,Takeshi NAKAI: "Unique Stereocontrol in Lanthanide (III)-Catalysed Aldol Reactions with the Ketene Silyl Acetal of Methyl (R)-3-Hydroxyburanoate" Tetrahedron Letters. 33. 1465-1468 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Jin-Hua GU,Mikako OKAMOTO,Masahiro TERADA,Koichi MIKAMI,Takeshi NAKAI: "Unique Stereocontrol in Europium(III)-Catalyzed Cyanosilylation of Chiral α-Alkoxy and α-Amino Aldehydrs" Chemistry Letters. 1169-1172 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Seiichi AOKI,Koichi MIKAMI,Masahiro TERADA,Takeshi NAKAI: "Enantio- and Diastereoselective Catalysis of Addition Reaction of Allylic Silanes and Stannanes to Glyoxylates by Binaphthol-Derived Tiranium Complex." Tetrahedron. (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 中井 武: "有機合成反応の触媒的立体化学制御-CHEMIZYMEの創製をめざして-" 現代化学増刊. 21. 195-213 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Takeshi NAKAI(分担執筆): "Organic Synthesis in Japan: Past,Present,and Future" 有機合成化学協会, 565 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Catalytic Asymmetric Glyoxylate-Ene Reaction: A Practical Access to alpha-Hydroxy Esters in High Enantiomeric Purities" J.Am.Chem.Soc. 112. 3949-3954 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro Terada: "Remarkable Positive Nonlenear Effect in the Enantioselective Glyoxylate-Ebe Reaction Catalyzed by a Chiral Titanium Complex" J.Chem.Soc.Chem.Commun. 22. 1623-1624 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Carbonyl-Ene Reaction with Vinylsilanes: Silicon As a Controlling Element for the Stereo- and Regiochemistry" J.Am.Chem.Soc. 112. 6737-6738 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Carbonyl-Ene Reaction: A New Method for Acyclic Stereocontrol" J.Synth.Org.Chem.,Jpn. 48. 292-303 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Creation of "Chemzyme": Development of Asymmetric Catalytic Carbonyl-Ene Reactions" Oil Chemistry. 39. 129-237 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro Terada: "Enantioselective Hetero-Diels-Alder Reaction with Glyoxylate Catalyzed by Chiral Titanium Complex: Asymmetric Synthesis of the Lactone Portion of Mevinolin and Compactin" Tetrahedron Lett. 32. 935-938 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Unique Catalysis by Eu(dppm)_3: Catalytic Molecular Recognition in Aldol and Michael Reaction" J.Org.Chem. 55. 5456-5459 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Lanthanide(III) Catalyzed Aldol Reactions of Glyceraldehyde Acetonide with Ketene Silyl Acetals: Catalytic Asymmetric Route to Monosaccharides" Tetrahedron:Asymmetry. 2. 993-996 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Chiral Titanium Complex-Catalyzed Dields-Alder Reaction: A Potential Route to Anthracyclie Intermediates" Terahedron:Asymmetry. 2. 643-646 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Asymmetric Catalysis by chiral Titanium Perchlorate for Carbonyl-Ene Reaction" Tetrahedron Lett. 32. 6571-6574 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Asymmetric Catalysis of Ene Reactions" Kagaku (Chemistry). 46. 138-139 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro Terada: "Stereo-Modulating Catalysis by Europium (III) Aldehydes with Ketene Silyl Acetals" Chemistry Lett. 29-32 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Mikami: "Asymmetric Catalysis for Carbonyl-Ene Reaction" Synlett. 255-265 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Jin-Hua Gu: "Unique Stereocontrol in Lanthanide(III)-Catalyzed Aldol Reactions with Ketene Silyl Acetal of Methyl (R)-3-Hydroxybutanoate" Tetrahedron Lett. 33. 1465-1468 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Jin-Hua Gu: "Unique Stereocontrol in Europium(III)-Catalyzed Canosilylation of Chiral alpha-Amino Aldehydes" Chemistry Lett. 1169-1172 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Seiichi Aoki: "Enantio-and Diastereoselective Catalysis of Addition Reaction of Allylic Silanes abd Stannanes to Glyoxylates Catalyzed by Binaphthol-Derived Titanium Complex" Tetrahedron.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Takeshi Nakai: "Catalytic Stereocontrol in Synthetic Organic Reactions: Creation of "Chemzyme"" Gendai Kagaku (Modern Chemistry). 21. 195-213 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Takeshi Nakai: Organic Synthesis in Japan: Past, Present, and Future. Pericyclic Approach to Stereochemical Control: Acyclic Stereocontrol via [2,3]Wittig Rearrangement and Asymmetric Catalysis of Glyoxylate-Ene Reaction, 267-274 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Masahiro TERADA,Jin-Hua GU,Dibakar C.DEKA,Koichi MIKAMI,Takishi NAKAI: "Stiteo-Modulating Catalysis by Europium(III)Complexes in Aldol Riactions of Cheral α-Alkoxy Aldihydis with Ketene Silyl Acetals" Chemistry Letters. 29-32 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Koechi MIKAMI,Masahiro TERADA,Satoshe NARISAWA,Takeshi NAKAI: "Asymmetric Catalysis for Carbonyl-Ene Reaction" Synlett. 255-265 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] jin-Hua Gu,Masahiro TERADA,Koichi MIKAMI,Takeshi NAKAI: "Unique Steteocontrol in Lanthanide(III)-Catalysed Aldol Reactions with the Ketene Silyl Acetal of Methyl (R)-3-Hydroxybutanoate" Tetrahedron Letters. 33. 1465-1468 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] jin-Hua Gu,Mikako OKAMOTO,Masahiro TERADA,Koichi MIKAMI,Takishi NAKAI: "Unique Stereocontrol in Europium(III)-Catalyzed Cyanosilylation of Chiral α-Alkoxy ans α-Amino Aldehydes" Chemistry Letteos. 1169-1172 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Seiichi AOKI,Koiche MIKAMI,Masahiro TERADA,Takeshi NAKAI: "Enantio-and Diastereoselective Catalysis of Addition Reaction of Allylic Silanes ans Stannanes to Glyoxylates by Binaphthol-Derived Titanium Complex." Tetrahedron. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] 中井 武: "有機合成反応の触媒的立体化学制御-CHEMIZYMEの創製をめざして-" 現代化学増刊. 21. 195-213 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Takeshi NAKAI(分担執筆): "Organic Synthesis in Japan:Past,Present,and Future" 有機合成化学協会, 565 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Masahiro TERADA,Koichi MIKAMI,Takeshi NAKAI: "Enantioselective HeteroーDielsーAlder Reaction with Glyoxylate Catalyzed by Chiral Titanium Complex:Asymmetric Synthesis of the Lactone Portion of Mevinolin and Compactin" Tetrahedron Letters. 32. 935-938 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Takeshi NAKAI: "Unique Catalysis by Eu(dppm)_3:Catalytic Molecular Recognition in Aldol and Michael Reaction" Journal of Organic Chemistry. 56. 5456-5459 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Takeshi NAKAI: "Lanthanide(III)Catalyzed Aldol Reactions of Glyceraldehyde Acetonide with Ketene Silyl Acetals:Catalytic Asymmetric Route to Monosaccharides" Tetrahedron Asymmetry. 2. 993-996 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Yukihiro MOTOYAMA,Takeshi NAKAI: "Chiral Titanium ComplexーCatalyzed Diels Alder Reaction:A Potential Route to Anthracycline Intermediates" Tetrahedron Asymmetry. 2. 643-646 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Koichi MIKAMI,Masahiro TERADA,Eiji SAWA,Takeshi NAKAI: "Asymmetric Catalysis by Chiral Titanium Perchlorate for CarbonylーEne Cycization" Tetrahedron Letter. 32. 6571-6574 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 三上 幸一,寺田 眞浩,成沢 智司,中井 武: "エン反応の不斉触媒化" 化学. 46. 138-139 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Ko^^ーichi Mikami: "Catalytic Asymmetric GlyoxylateーEne Reaction:A Practical Access to αーHydroxy Esters in High Enantiomeric Purities" Journal of American Chemical Society. 112. 3949-3954 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Masahiro Terada: "Remarkable Positive Nonlinear Effect in the Enantioselective GlyoxylateーEne Reaction Catalysed by a Chiral Titanium Complex" Chemical Communications. 22. 1623-1624 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Ko^^ーichi Mikami: "CarbonylーEne Reaction with Vinylsilanes:Silicon As a Controlling Element for the Stereoーand Regiochemisty" Journal of American Chemical Society. 112. 6737-6738 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Fumiyuki Shirai: "Diastereofacial Selection in Titanium TetrachlorideーPromoted Aldol Reactions with the Silyl Ketene Acetal of Methyl (R)ー3ーHydroxybutanoate" Chemistry Letters. 1931-1934 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 三上 幸一: "カルボニルーエン反応:新しい鎖状立体制御法" 有機合成化学協会誌. 48. 292-303 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 三上 幸一: "“Chemzyme"の創製,不斉触媒的カルボニルーエン反応の開発をケ-ス・スタディ-として" 油化学. 39. 129-137 (1990)

    • Related Report
      1990 Annual Research Report

URL: 

Published: 1990-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi