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

Development of Highly Efficient and Selective Chirality Transfer Reaction

Research Project

Project/Area Number 63570990
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

IBUKA Toshiro  Faculty of Pharmaceutical Sciences, Kyoto University, Associate Professor, 薬学部, 助教授 (80025692)

Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1989: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1988: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsOrganocopper / Transition Metal / Lewis Acid / Asymmetric Synthesis / Quaternary Carbon / 1,3-Chirality Transfer / S_N2' Reaction / Organocopper-Lewis Acid Complex / S_N2'反応 / キラリティ / 不斉転位反応 / 有機銅ールイス酸複合剤 / 立体選択的合成
Research Abstract

Development of synthetic methods which provide ready access to chiral carbon centers with a high level of regio-, chemo-, and stereo-control as well as high chemical and optical yields represents a contemporary challenge for synthetic organic chemists. Recently, great advances have been made in the alpha-alkylation of esters and their congeners in enantio- or diastereoselective reactions via chiral metal enolates, chiral oxazolines, intra- and extraannular chirality transfer reactions, asymmetric hydrogenations, enzyme-catalyzed reactions, sigmatropic rearrangements such as the Ireland-Claisen rearrangement, and photodeconjugation of alpha,beta-enoates.
Chiral alpha-substituted delta-oxygenated beta,gamma-enoates bearing an (E)-double bond are promising intermediates for the synthesis of natural products since both protected (E)-allylic alcohol and ester functions are available for further chemical manipulation. However, in contrast to the well documented methodologies mentioned above, … More chiral syntheses of such a- alkyl-(E)-beta,gamma-enoates remain a challenge.
Reaction of gamma-mesyloxy-(E)- or (Z)-alpha, beta-enoates with Me_2Cu(CN)Li_2.BF_3 (prepared. from MeLi-LiI in ether), MeCu(CN)Li.BF_3 (prepared from MeLi-LiBr in ether), and RCu(CN)Li.BF_3 (R = Et, n-Pr, n-Bu) in tetrahydrofuran or mixed solvents involving tetrahydrofuran at - 78゚C results in the formation of synthetically useful alpha-alkyl-(E)-beta,gamma-enoates, compounds that are not easily accessible by other means. In all cases the chemical and optical yields are very high. The method can be applied to the synthesis of chiral quatemary carbon center with very high optical purity. Furthermore, an efficient synthetic route of protected homochiral divinylmethanols from L- and D-tartrates with organocyanocopper-boron trifluoride complexes mediated 1,3-chirality transfer reaction has been developed. The chemical yield and optical purity have been found to be unformly very high. The (E)-geometry of the product is not related to the geometry of the starting material. Addition of BF_3.Et_2O to the organocopper reagent is critical to the clean 1,3-chirality transfer. Other essential factors such as reaction solvent, type of organocopper reagent, and nature of the gamma-oxygenated leaving group are discussed. The (E)-geometry of the beta,gamma-double bond of the alkylation products could be determined by ^1H NMR spectroscopy using a chiral shift reagent. The present 1,3-chirality transfer strategy is a potentially useful method for the synthesis of biologically important compounds such as pheromones, isostares, and antibiotics. Less

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] 山本嘉則、西井真二、井深俊郎: "Acyclic Stereocontrol via an Electron Transfer Process.Remarkable Stereochemical Difference between One-and Two-Electron Events." J.Am.Chem.Soc.110. 617-618 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、西井真二、山本嘉則: "A Convenient Synthesis of Four Stereoisomeric Methyl 2-Htdroxy-3-tert-Butyldimethylsiloxybutanoates from L-and D-Threonines.Versatile Chiral Building Blocks." Chemistry Express. 3. 53-56 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 山本嘉則、井深俊郎: "Recent Progress in Asymmertric Synthesis via Organocopper Compounds." GIT Fachz.Lab.32. 961-972 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、斎藤真子、多賀徹、西井真二、新宮徹朗、山本嘉則: "New Stereoselective Synthesis of 20S and 20R Steroidal Side Chains.Remarkable Stereoselectivity Differences between Saturated and α,β-Unsaturated Steroidal Esters." J.Org.Chem.53. 3947-3952 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、山本嘉則、多賀徹、西井真二: "A New Stereoselective Synthesis of(20R) and (20S)-Stereoidal Side Chains." J.Chem.Soc.,Chem..Commum.342-344 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、田中みわ、山本嘉則: "A Regio-,(E)-Stereo-,and Chemo-selective Synthesis of Unsymmetrical Divinylmethanols starting from L- and D-Tartrates via Organocyanocopper Lewis Acid Mediated 1,3-Chirality Transfer." J.Chem.Soc.,Chem.Commun.967-969 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、西井真二、秋元直茂、山本嘉則、田中みわ: "Organocyanocopper-Trifluoroborane Mediated 1,3-Chirality Transfer Reaction of γ-Mesyloxy-α-alkyl-α,β-enoates for the Construction of Chiral Quaternary with High Optical Purity" J.Org.Chem.54. 4055-4061 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、西井真二、田中みわ、山本嘉則: "Very High Chemoselective,and (E)-Stereoselective 1,3-Chirality Transfer Involving Reaction of Acyclic(E)-and(Z)-γ-Mesyloxy-α,β-enoates and Organocopper Trifluroboborane Reagents" J.Am.Chem.Soc.111. 4864-4872 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 井深俊郎、根本尚夫、田中みわ、山本嘉則: "Regio-and Stereoselective in the Reaction of Methyl 4,5-Epoxy-2-hexenoate with Methylcopper Reagents." Tetrahedron. 45. 435-442 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 山本嘉則、西井真二、井深俊郎、: "Diastereofacial Selection in the Conjugate Addition of γ-Alkyl-α,β-Unsaturated Carbonyl Derivatives.Stereocontrol Dictated by Aromatic Ring- Palladium Interaction." J.Chem.Soc.,Perkin Trans.1.1703-1705 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yoshinori Yamamoto, Shinji Nishii, and Toshiro Ibuka: "Acyclic Stereocontrol via an Electron Transfer Process. Remarkable Stereochemical Difference between One- and Two-Electron Events." J. Am. Chem. Soc., 110, 617-618 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Shinji Nishii, and Yoshinori Yamamoto: "A Convenient Synthesis of Four Stereoisomeric Methyl 2-Hydroxy-3-tert-Butyldimethylsiloxybutanoates from L- and D-Threonines. Versatile Chiral Building Blocks for the Synthesis of Natural Products." Chem. Express, 3.53-56 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yoshinori Yamamoto and Toshiro Ibuka: "Recent Progress in Asymmetric Synthesis via Organocopper Compounds." GIT Fachz. Lab., 32, 961-972 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Tooru Taga, Tetsuro Shingu, Masako Saito, Shinji Nishii, and Yoshinori Yamamoto: "New Stereoselective Synthesis of 20S and 20R Steroidal Side Chains. Remarkable Stereoselectivity Differences between Saturated and alpha,beta-Unsaturated Steroidal Esters." J. Org. Chem., 53, 3947-3952 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Tooru Taga, Shinji Nishii, and Yoshinori Yamamoto: "A New Stereoselective Synthesis of (20R)- and (20S)- Steroidal Side Chains." J. Chem. Soc., Chem. Commun., 342-344 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Miwa Tanaka, and Yoshinori Yamamoto: "A Regio-. (E)-Stereo-, and Chemo-selective Synthesis of Unsymmetrical Divinylmethanols starting from L- and D-Tartrates via Organocyanocopper Lewis Acid Mediated 1,3-Chirality Transfer." J. Chem. Soc., Chem. Commun., 967-969 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Naoshige Akimoto, Miwa Tanaka, Shinji Nishii, and Yoshinori Yamamoto: "Organocyanocopper-Trifluoroborane Mediated 1,3-Chirality Transfer Reaction of lambda-Mesyloxy-alpha-alkyl-alpha,beta-enoates for the Construction of Chiral Quaternary Carbon Centers with High Optical Purity." J. Org. Chem., 54, 4055-4061 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Miwa Tanaka, Shinji Nishii, and Yoshinori Yamamoto: "Very High Chemoselective, Regioselective, and (E)-Stereoselective 1,3-Chirality Transfer Involving Reaction of Acyclic (E)- and (Z)-lambda-Mesyloxy-alpha,beta-Enoates and Organocopper Trifluoroborane Reagents." J. Am. Chem. Soc., 111, 4864-4872 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Ibuka, Miwa Tanaka, Hisao Nemoto, and Yoshinori Yamamoto: "Regio- and Stereo-selectivity in the Reaction of Methyl 4,5-Epoxy-2-hexenoate with Methylcopper Reagents." Tetrahedron 45, 435-442 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yoshinori Yamamoto, Shinji Nishii, and Toshiro Ibuka: "Diastereofacial Selection in the Conjugate Addition of lambda-Alkyl-alpha,beta-Unsaturated Carbonyl Derivatives. Stereocontrol Doctated by Aromatic Ring-Palladium Interaction." J. Chem. Soc., Perkin Trans. 1 1703-1705(1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 山本嘉則,西井真二,井深俊郎: "Acyclic Stereocontrol via an Electron Transfer Process.Remarkable Stereochemical Difference between One-and Two-Electron Events." J.Am.Chem.Soc.110. 617-618 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] 井深俊郎,西井真二,山本嘉則: "A Convenient Synthesis of Four Stereoisomeric Methyl 2-Hydroxy-3-tert-Butyldimethylsiloxybutanoates from L-and D-Threonines.Versatile Chiral Building Blocks." Chemistry Express. 3. 53-56 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] 山本嘉則,井深俊郎: "Recent Progress in Asymmetric Synthesis via Organocopper Compounds." GIT Fachz.Lab.32. 961-972 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] 井深俊郎,斉藤真子,多賀徹,西井真二,新宮徹朗,山本嘉則: "New Stereoselective Synthesis of 20S and 20R Steroidal Side Chains.Remarkable Stereoselectivity Differences between Saturated and α,β-Unsaturated Steroidal Esters." J.Org.Chem.53. 3947-3952 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] 井深俊郎,山本嘉則,多賀徹,西井真二: "A New Stereoselective Synthesis of (20R)and(20S)-Steroidal Side Chains." J.Chem.Soc.,Chem..Commun.342-344 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] 井深俊郎,田中みわ,山本嘉則: "A Regio-,(E)-Stereo-,and Chemo-selective Synthesis of Unsymmetrical Divinylmethanols starting from L-and D-Tartrates via Organocyanocopper Lewis Acid Mediated 1,3-Chirality Transfer." J.Chem.Soc.,Chem.Commun.967-969 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] 井深俊郎: J.Chem.Soc.,Chem.Commun.342-344 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 井深俊郎: Chemistry Express. 3. 53-56 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 井深俊郎: J.Org.Chem.53. 3947-3952 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 井深俊郎: Tetrahedron. 45. 435-442 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 山本嘉則: J.Am.Chem.Soc.110. 617-618 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 山本嘉則: "Chemie-Biochemie:Chiralitat" G.I.T.Verlag, 119-133 (1988)

    • Related Report
      1988 Annual Research Report

URL: 

Published: 1988-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi