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Development of Transition-metal Catalyzed Amination Process of Olefins Aimed for the Production of Physiologically Important Compounds

Research Project

Project/Area Number 05555246
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionNagasaki University

Principal Investigator

TAMARU Yoshinao  Nagasaki University Fac.of Engineering Professor, 工学部, 教授 (80026319)

Co-Investigator(Kenkyū-buntansha) NISI Seiichi  Ajinomoto CO.LTD.Researcher, 東海工場技術部, 研究員
TANAKA Shuji  Nagasaki University Fac.of Engineering Associate Professor, 工学部, 助教授 (80217033)
普神 敬悟  長崎大学, 工学部, 助手 (90202283)
Project Period (FY) 1993 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥15,100,000 (Direct Cost: ¥15,100,000)
Fiscal Year 1995: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1994: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1993: ¥7,000,000 (Direct Cost: ¥7,000,000)
KeywordsAminocarbonylation / Palladium Catalysis / Carbon monoxide / Chemoselectivity / Carbamate (endo-, exo-) / Urea / ジエニルアミノ化 / 一酸化炭素 / アリルアミン
Research Abstract

exo-Ureas, endo-ureas, exo-sulfonamides, and exo-carbamates readily undergo aminocarbonylation by the catalysis of PdC12 in methanol under 1 atm of carbon monoxide at room temperature. O-Allyl-endo-carbamates, on the other hand, do not undergo the aminocarbonylation under the similar conditions. This makes sharp contrast to the fact that endo-ureas are more reactive toward aminocarbonylation than exo-ureas. After experimentations, we found that aminocarbonylation of endo-carbamates proceed smoothly in the presence of sodium acetate and methyl orthoacetate (MOA). MOA can be utilized as an additive (in MeOH as a solvent) or as a solvent. In the latter case, MOA serves not only as a solvent but also as a reactant (a nucleophile) and much higher stereoselectivities are observed then the case undertaken in MOA/MeOH.Diamines possessing endo-carbamate and exo-carbamate (exo-urea or exo-sulfonamide) moieties in the same molecules were found to undergo chemoselective amination : the endo-carbamate moieties in MOA and the exo-carbamate, exo-urea, and exo-sulfonamide moieties in MeOH undergo the selective aminocarbonylation under 1 atm of CO by the catalysis of PbC12.

Report

(4 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (40 results)

All Other

All Publications (40 results)

  • [Publications] M.Kimura, S.Tanaka, and Y.Tamaru: "Silver(I) Catalyzed Aminocyclization of 2,3-Butadienyl and 3,4-Pentadienyl Carbamates: An efficient and Steroselective Synthesis..." Bull. Chem. Soc. Jpn.68. 1689-1705 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] y.Tamaru, A.Tanaka, K.Yasui, S.Goto, S.Tanaka: "Highly Stereoselective Allylation of Aldehyde: Generation of Stereochemically Sefined Allylzinc Species via Alkyl-Allyl Exchange..." Angew. Chem. Int. Ed. Engl.34. 787-789 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Yasui, K.Fugami, S.Tanaka, and Y.Tamaru: "Unsymmtrical Ketone Synthesis via Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide'" J. Org. Chem.60. 1365-1380 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura, S.Tanaka, and Y.Tamaru: "Palladium Catalyzed Stereoselective Allylaminocyclization and (1,3-Butadien-2-yl)aminocyclization of 2,3-Butadienyl Tosylcarbamates" J. Org. Chem.60. 3764-3772 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Yasui, S.Tanaka, and Y.Tamaru: "Stereoselective Synthesis of Cyclopropanone Ketals via Silyl Chloride Promoted Cyclization of β-Zinciopropionates"." Tetrahedrem. 51. 6881-6900 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru, H.Harayama, T.Bando, H.Nagaoka...: "Pronounced Electronic Effect of Allylic Amino Groups on the π-Facial Stereoselectivity and Reactivity of the Iodoetherification of...." Liebigs Ann.223-234 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru: "(3-Ethoxy-3-oxopropyl)iodozinc"(Tamaru's Reagent)in Encyclopeida of Reagents for Organic Synthesis"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru: "Advances of Detailed Reaction Mechanisms, Ed. J. M. Coxon, Vol.4, Chapter2"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 田丸良直: "Advances of Detaited Reaotim Mechanism" JAI press, 32 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura, S.Tanaka, and Y.Tamaru: "Silver (I) Catalyzed Aminocyclization of 2,3-Butadienyl and 3,4-pentadienyl carbamates : An Efficient and Stereoselective Synthesis of 4-Vinyl-2-oxazolidinones and 4-Vinyltetrahydro-1,3-oxazin-2-ones." Bull.Chem.Soc.Jpn.68. 1689-1705 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru, A.Tanaka, K.Yasui, S.Goto, and S.Tanaka: "Highly Stereoselective Allylation of Aldehyde : Generation of Stereochemically Defined Allylzinc Species via Alkyl-allyl Exchange Reaction between pi-Allylpalladium and Diethylzinc" Angew.Chem., Int.Ed.Engl.34. 787-789 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Yasui, K.Fugami, S.Tanaka, and Y.Tamaru: "Unsymmtrical Ketone Synthesis via Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide" J.Org.Chem.60. 1365-1380 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura, S.Tanaka, and Y.Tamaru: "Palladium Catalyzed Stereoselective Allylaminocyclization and (1,3-Butadien-2-yl) amino-cyclization of 2,3-Butadienyl Tosylcarbamates" J.Org.Chem.60. 3764-3772 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Yasui, S.Tanaka, and Y.Tamaru: "Stereoselective Synthesis of Cyclopropanone Ketals via Silyl Chloride Promoted Cyclization of beta-Zinciopropionates." Tetrahedron. 51. 6881-6900 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru, H.Harayama, T.Bando, H.Nagaoka, and Z.Yoshida: "Pronounced Electronic Effect of Allylic Amino Groups on the pi-Facial Stereoselectivity and Reactivity of the Iodoetherification of N-Substituted 3-Amino-4-penten-1-ols." Liebigs Ann. 223-234 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru, S.Goto, A.Tanaka, M.Shimizu, and M.Kimura: "Propargylation of Carbonyl Compounds via Umpolung of Propargylpalladium with Diethlzinc" Angew.Chem.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru: "(3-Ethoxy-3-oxopropyl) iodozinc (Tamaru's Reagent)" Encyclopedia of Reagents for Organic Synthesis, Ed.L.A.Paquette, Wiley, Chichester. Vol.4. 2366-2369 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru and K.Fugami: "Urea" Encyclopedia of Reagents for Organic Synthesis, Ed.L.A.Paquette, Wiley, Chichester. Vol.8. 5472-5475 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru: "Unique Reaction Behavior of Organozincs toward pi-Allylpalladium Complexes : Palladium Catalyzed Synthesis of Unsymmetrical Ketones and Umpolung of pi-Allylpalladium." Journal of Synthetic Organic Chemistry, Japan. 53. 1102-1113 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Tamaru: "Unique Reactivity of Functionalized Organozincs" Advances of Detailed Reaction Mechanisms, Ed.J.M.Coxon, Vol.4, Chapter 2. JAI press, 41-72 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kimura: "Silver (I) Catalyzed Aminocyclization of 2,3-Butadienyl and 3,4-Pentadienyl Carbamates : An Efficient and Stereoselective Synthesis of・・・・・・" Bull.Chem.Soc.Jpn.68. 1689-1705 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y.Tamaru: "Highly Stereoselective Allylation of Aldehyde : Generation of Stereochemically Defined Allylzinc Species via Alkyl-Allyl Exchange Reaction・・・・・・" Angew.Chem.Int.Ed.Engl.34. 787-789 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Yasui: "Unsymmtrical Ketone Synthesis via Three-Component Connection Reaction of Organozincs,Allylating Agents,and Carbon Monoxide" J.Org.Chem. 60. 1365-1380 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Kimura: "Palladium Catalyzed Stereoselective Allylaminocyclization and (1,3-Butadien-2-yl) aminocyclization of 2,3-Butadienyl Tosylcarbamates" J.Org.Chem. 60. 3764-3772 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Yasui: "Stereoselective Synthesis of Cyclopropanone Ketals via Silyl Chloride Promoted Cyclization of β-Zinciopropionates" Tetrahedron. 51. 6881-6900 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y.Tamaru: "Pronounced Electronic Effect of Allylic Amino Groups on the π-Facial Stereoselectivity and Reactivity of the Iodoetherification of N-Substituted・・・・・・" Liebigs Ann.(印刷中).

    • Related Report
      1995 Annual Research Report
  • [Publications] Y.Tamaru: "Tamaru's Reagent in “Encyclopedia of Reagents for Organic Synthesis"" Wiley, 4 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y.Tamaru: "“Advances of Detailed Reaction Mechanisms"" JAI press, 32 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.Bando: "Regio-and Stereoselective Synthesis of 1,3-Hydroxy Amines via Palladium-catalyzed Carbonate-Carbamate Trnsformation with Unique Stereoselectivity" J.Org.Chem.59. 1465-1474 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Ono: "Palladium Catalyzed Arylation of N-Alkyl O-Aryl Carbamates:Synthesis of Cinnamy Alcohols via Heck Arylation" Tefrahedrm Lett. 35. 4133-4136 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Kimura: "Palladium(2+) Catalyzed 5-endo-trigonal Cyclization of 2-Hydroxy-3-butenylamines:Synthesis of Five-Membered Nitrogen Heterocycles" J.Chem.SOC.Chem.Conrnun. 2531-2533 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Tamaru: "Convenient Synthesis of 4-Methylene-1,3-oxazolidin-2-ones and 4-Methylene-1,3-oxazin-2-ones via Transition-metal Catalyzed Intramolecular Addition of・・・" Bull.Chem.Soc.Jpn.67. 2838-2849 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Tamaru: "Highly Stereoselective Allylation of Aldehdye:Generation of Stereochemically Defined Allylzinc Species via Alkyl-Ally Exchange Reaction between π-Allyl・・・" Angew.Chem. (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Yasui: "Unsymmtrical Ketone Synthesis via Three-Component Connection Reaction of Organozince,Allylating Agents,and Carbon Monoxide" J.Org.Chem. (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Tamaru: "Tamaru's Reagent in "Encyclopedia of Reagents for Organic Synthesis"" Johv Wiley&Sons, (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Tamaru: "Urea in "Encyclopedia of Reagents for Organic Synthesis"" Johv Wiley&Sons, (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Tamaru: "Pronouced Electonic Effects of Allylic Amino Group on the pi‐Facial Stereoseletivity and Reactivity in Electrophilic Addition Reaction to Double Bonds" J.Chem.Soc.,Chem.Commun.,. 21. 1601-1602 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Kimura: "Pd^<2+>‐catalyzed Oxidative Aminocarbonylation of O‐2,3‐Butadienyl and O‐3,4‐Pentadienyl N‐Tosylcarbamates" Tetrahedron Lett.,34. 47. 7611-7614 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Yasui: "Use of pi‐Allylpalladium as a Nucleophile via an Alkyl‐Allyl Exchange Reaction with Alkylzinc" Tetrahedron Lett.,34. 47. 7619-7622 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Bando: "Regio‐and Stereoselective Synthesis of 1,3‐Hydroxy Amines via Palladiun‐catalyzed Carbonate‐Carbamate Transformation with Unique Stereoselectivity" J.Org.Chem.(in press). (1994)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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