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Direct synthetic method for preparation of organotitanium complexes and their synthetic utility

Research Project

Project/Area Number 07455359
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionTOKYO INSTITUTE OF TECHNOLOGY

Principal Investigator

SATO Fumie  TOKYO INSTITUTE OF TECHNOLOGY,Biosci. & Biotech., Professor, 生命理工学部, 教授 (50016606)

Co-Investigator(Kenkyū-buntansha) OKAMOTO Sentaro  TOKYO INSTITUTE OF TECHNOLOGY,Biosci.& Biotech., Assistant Professor, 生命理工学部, 助手 (00201989)
URABE Hirokazu  TOKYO INSTITUTE OF TECHNOLOGY,Biosci.& Biotech., Assistant Professor, 生命理工学部, 助手 (10176745)
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1996: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1995: ¥5,200,000 (Direct Cost: ¥5,200,000)
KeywordsTitanium / Nucleophilicacyl substitution / Ester / Heterocycle / Chiral / Allyltitanium / Aminoacid / Cyclic compound / アリルアルコール / アレン / 有機チタン化合物 / アリルチタン / プロパルギルチタン / アレニルチタン / アセチレン錯体 / 酸化的付加 / アリルアミン
Research Abstract

Organic synthesis using titanium (II) complexes has remained unexplored because of the lack of a practical method for synthesis of them. Recently, we have found that the reacition of Ti (O-i-Pr)_4 with 2 equivalent of i-PrMgX provides (eta^2-propene) Ti (O-i-Pr)_2 (1) in essentially quantitative yield and it acts as versatile titanium (II) equivalent. We have now revealed the following synthetically useful reactions using 1.
1) Reaction of cyclic allylic compounds with 1 provides the corresponding cyclic allyltitanium complexes, which in turn react with aldehydes and imines highly stereoselectively.
2) Reaction of 1 with unsaturated esters or carbonates results in intramolecular acyl substitution reaction, thus opening up a new entry cyclic compounds, including N-heterocycles.
3) 1 reacts with alkynes to afford titanium-alkyne complexes which in turn react with optically active aldehydes stereoselectively afforeling allylic alcohols in chiral form.
4) Intramolecular acyl substitution of allenylic carbonates affords a new methodology for synthesizing optically active compounds

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] Aleksandr Kasatkin: "New,Efficient Method for the Synthesis of Allyltitanium Compounds from Allyl Halides or Allyl Alcohol Derivatives via Oxidative Addition. A Highly Efficient and Practical Synthesis of Homoallyl Alcoholsl" J. Am. Chem. Soc.117,13. 3881-3882 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by XTi(O-i-Pr)_3(X=Cl,O-i-Pr)/2i-PrMgBr Reagent. Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounds" J. Am. Chem. Soc.118,9. 2208-2216 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Reactions of β,γ-and γ,δ-Unsaturated Esters with Ti(OiPr)_4/2iPrMgCl Reagent. Formation of β-Titanated Esters,β-Titanated Cyclobutanones or Acyltitanium Compounds" Angew. Chem.108,17. 2091-2093 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Reactions of β,γ-and γ,δ-Unsaturated Esters with Ti(OiPr)_4/2iPrMgCl Reagent. Formation of β-Titanated Esters,β-Titanated Cyclobutanones or Acyltitanium Compounds" Angew. Chem. Int. Ed. Engl.35,17. 1966-1968 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ken Suzuki: "A Novel Tandem Cyclization of 2,7-or 2,8-Bis-unsaturated Esters Mediated by (η^2-Propene)TiX_2(X=Clor O-i-Pr). A Facile Construction of Bicyclo[3.3.0]octane,-[4.3.0]nonane and-[3.1.0]hexane Skeletons" J. Am. Chem. Soc.118,36. 8729-8730 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Unusual Regiose lectivity Controlled by Steric Strain in Carbonyl Addition Reaction of Allyl-or Allenyl-/Propargyltitanium Compounds. Efficient Method for Synthesis of Alkylidenecyclopropane Derivatives" Angew. Chem.108,23/24. 3024 3025 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Unusual Regiose lectivity Controlled by Steric Strain in Carbonyl Addition Reaction of Allyl-or Allenyl-/Propargyltitanium Compounds. Efficient Method for Synthesis of Alkylidenecyclopropane Derivatives" Amgew. Chem. Int. Ed. Engl.35,23. 2848 2849 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Yuuki Takayama: "Titanium(II)-Mediated Intramolecular Cyclization Reaction of 2,7-or 2,8-Bis-Unsaturated Carbonates and Acetates. A New and Afficient Method for Synthesis of Cycloalkane Compounds." Angew. Chem. Angew. Chem. Int. Ed. Engl.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "New, Efficient Method for the Synthesis of Allyltitanium Compounds from Allyl Halides or Allyl Alcohol Derivatives via Oxidative Addition. A Highly Efficient and Practical Synthesis of Homoallyl Alcohols 1" J.Am.Chem.Soc.117,13. 3881-3882 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Acyl Substitution Reactins Mediated by XTi (O-i-Pr)_3 (X=Cl, O-i-Pr) /2i-PrMgBr Reagent. Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounds" J.Am.Chem.Soc.118,9. 2208-2216 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Reactions of beta, gamma-and gamma., delta-Unsaturated Esters with Ti (OiPr)_4/2iPrMgCl Reagent. Formation of beta-Titanated Esters, beta-Titanated Cyclobutanones or Acyltitanium Compounds" Angew.Chem.108,17. 2091-2093 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Reactions of beta, gamma-and gamma., delta-Unsaturated Esters with Ti (OiPr)_4/2iPrMgCl Reagent. Formation of beta-Titanated Esters, beta-Titanated Cyclobutanones or Acyltitanium Compounds" Angew.Chem.Int.Ed.Engl.35,17. 1966-1968 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ken Suzuki: "A Novel Tandem Cyclization of 2,7-or 2,8-Bis-unsaturated Esters Mediated by (eta^2-Propene) TiX_2 (X=Cl or O-i-Pr). A Facile Construction of Bicyclo [3.3.0]octane, - [4.3.0] nonane and - [3.1.0] hexane Skeletons" J.Am.Chem.Soc.118,36. 8729-8730 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Unusual Regioselectivity Controlled by Steric Strain in Carbonyl Addition Reaction of Allyl- or Allenyl-/Propargyltitanium Compounds. Efficient Method for Synthesis of Alkylidenecyclopropane Derivatives" Angew.Chem.108,23/24. 3024-3025 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Aleksandr Kasatkin: "Unusual Regioselectivity Controlled by Steric Strain in Carbonyl Addition Reaction of Allyl- or Allenyl-/Propargyltitanium Compounds. Efficient Method for Synthesis of of Alkylidenecyclopropane Derivatives" Angew.Chem.Int.Ed.Engl.35,23. 2848-2849 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Yuuki Takayama: "Titanium (II) -Mediated Intramolecular Cyclization Reaction of 2,7- or 2,8-Bis-Unsaturated Carbonates and Acetates. A New and Afficient Method for Synthesis of Cycloalkane Compounds." Angew.Chem., Angew.Chem.Int.Ed.Engl.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by XTi(O-i-Pr)_3(X=Cl,O-i-Pr)/2i-PrMgBr Reagent.Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounds" J.Am.Chem.Soc.118,9. 2208-2216 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yukio Yoshida: "Intramolecular Carbon-Carbon Bond Forming Reactions Mediated by XTi(OPr-i)_3(X=Cl or OPr-i)/2i-PrMgBr Reagent Efficiert Synthesis of Cyclopentanols Having an Ethenylideneor Alkynyl Moiety at the β-Position" SYNLETT. 5. 437-438 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Aleksandr Kasatkin: "Reactions of β,γ-and γ,δ-Unsaturated Esters with Ti(OiPr)_4/2iPrMgCl Reagent.Formation of β-Titanated Esters, β-Titanated Cyclobutanones or Acyltitanium Compounds" Angew.Chem.108,17. 2091-2093 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Aleksandr Kasatkin: "Reactions of β,γ-and γ,δ-Unsaturated Esters with Ti(OiPr)_4/2iPrMgCl Reagent.Formation of β-Titanated Esters, β-Titanated Cyclobutanones or Acyltitanium Compounds" Angew.Chem.Int.Ed.Engl.35,17. 1966-1968 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Ken Suzuki: "A Novel Tandem Cyclization of 2,7-or 2,8-Bisunsaturated Esters Mediated by(η^2-Propene)TiX_2(X=Cl or O-i-Pr).A Facile Construction of Bicyclo[3.3.0]octane,-[4.3.0]nonane and-[3.1.0]hexane Skeletons" J.Am.Chem.Soc.118,36. 8729-8730 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Aleksandr Kasatkin: "Unusual Regiose Lectivity Controlled by Steric Strain in Carbonyl Addition Reaction of Allyl-or Allenyl-/Propargyltitanium Compounds.Efficient Method for Synthesis of Alkylide necyclopropane Derivatives" Angew.Chem.108,23/24. 3024-3025 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Aleksandr Kasatkin: "Unusual Regiose Lectivity Controlled by Steric Strain in Carbonyl Addition Reaction of Allyl-or Allenyl-/Propargyltitanium Compounds.Efficient Method for Synthesis of Alkylide necyclopropane Derivatives" Angew.Chem.Int.Ed.Engl.35,23. 2848-2849 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Hirokazu Urabe: "Selective Reaction of Aldehydes with Bicyclic Titanacyclopentadienes or Titanacyclopentenes Prepared in Situ from 1,6-or 1,7-Diynes or Enynes and(η^2-Propene)Ti(O-i-Pr)_2" J.Org.Chem.61,20. 6756-6757 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yuan Gao: "Stereo-and Regioselective Generation of Alkenylzinc Reagents via Titanium-Catalyzed Hydrozincation of Internal Acetylenes" J. Org. Chem.60-2. 290-291 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Aleksandr Kasatkin: "New, Efficient Method for the Synthesis of Allyltitanium Compounds from Allyl Halides or Allyl Alcohol Derivatives via Oxidative Addition. A Highly Efficient and Practical Synthesis of Homoallyl Alcohols" J. Am. Chem. Soc. 117-3. 3881-3882 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yuan Gao: "Stereoselective Synthesis of Allylic Amines by the Reaction of Titanium-Alkyne Complexes with Imines." Tetrahedron Letters. 36-33. 5913-5916 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Aleksandr Kasatkin: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by Ti(OP_<r->^i)_4/2^i-PrMgBr Reagent. Synthesis of Vinyltitanium Compounds Having a Lactone and/or an Ester Group from Acetylenic Carbonates" Tetrahedron Letters. 36-34. 6075-6078 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Aleksandr kasatkin: "Diastereoselectives Synthesis of trans-1,2-Disubstituted Cyclopropanols from Homoallyl or Bis-Homoallyl Esters via Tandem Intramolecular Nucleophilic Acyl Substitution and Intramolecular Carbonyl Addition Reactions Mediated by Ti(OP_<r-i>)_4/2^i-PrMgBr Reagent" Tetrahedron Letters. 36-34. 6079-6082 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yuan Gao: "Highly Selective Asymmetric Synthesis of Homoallylic Amines with and without a β-Substituent by the Reaction of Allylic Titanium Compounds with Chiral Imines" J. Org. Chem.60-25. 8136-8137 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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