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Design of Novel Amphoteric Chiral Ligands and their Use for Catalytic Asymmetric Synthesis

Research Project

Project/Area Number 08640681
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionNagoya City University (1997)
Kyoto University (1996)

Principal Investigator

UOZUMI Yasuhiro  Nagoya City University, Faculty of Pharmaceutical Sciences Professor, 薬学部, 教授 (90201954)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1997: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1996: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsCatalytic Asymmetric Synthesis / Palladium (II) Catalyst / Astmmetric Wacker Reaction / Cyclization of o-Allylphenol / bisoxazoline-binaphthyl / 光学活性ビスオキサゾリン / boxax配位子
Research Abstract

New class of optically active phosphines and oxazolines having fuctional groups (e.g.carboxyl, hydroxy) were designed and prepared. Of the ligands, the bisoxazoline-binaphthyl derivatives found utility as chiral ligands for palladium (II)-catalyzed asymmetric Wacker-type Cyclization of o-allylphenols. Thus, catalytic asymmetric Wacker-type cyclization of 2-(2,3-dimethyl-2-butenyl) phenol in the presence of 10 mol % of a chiral palladium (II) catalyst prepared from Pd (OCOCF_3)_2 and (S,S)-2,2'-bis[4-(alkyl)oxazolyl]-1,1'-binaphthyl (S,S)-boxax) and rho-benzoquinone in methanol at 60゚C for 24h gave 75% yield of (S)-(-)-2-methyl-2-isopropenyl-2,3-dihydrobenzofuran of 96% ee.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] 林 民生: "Regio-and Enantioselective Allylic Alkylation Catalyzed by Chiral Monophosphine-Palladium Complexes" Chem.Commun.561-562 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 魚住 泰宏: "Catalytic Asymmetric Wacker-Type Cyclization" J.Am.Chem.Soc.119. 5063-5064 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 魚住 泰宏: "New Amphiphilic Palladium-Phosphine Complexes Bound to Solid Supports:Preparation and Use for Catalytic Allylic Substitution in Aqueous Media" Tetrahedron Lett.38. 3557-3560 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 林 民生: "Retention of Regiochemistry of Allylic Esters in Palladium-Catalyzed Allylic Alkylation in the Presence of a MOP Ligand" J.Am.Chem.Soc.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 川面 基: "Regiocontrol in Palladium-Catalysed Allylic Alkylation by Addition of Lithium Iodide" Chem.Commun.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 魚住 泰宏: "Asymmetric Aza-Claisen Rearrangement of Allyl Imidates Catalyzed by Homochiral Palladium(II)Complexes" Tetrahedron Asymmetry. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takashi Kamikawa, Yasuhiro Uozumi, and Tamio Hayashi: "Enantioposition-Selective Alkynylation of Biaryl Ditriflates by Palladium-Catalyzed Asymmetric Cross-Coupling" Tetrahedron Lett. 37. 3161-3164 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Kenji Kitayama, Hayato Tsuji, Yasuhiro Uozumi, and Tamio Hayashi: "Asymmetri Hydrosilylation of cyclic 1,3-Dienes Catalyzed by an Axially Chiral Monophosphine-palladium complex" Tetrahedron Lett. 37. 4169-4172 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Tamio Hayashi, Eiji Kishi, Vadim Soloshonok, and Yasuhiro Uozumi: "Erythro-Selective Aldol-Type Reaction of N-Sulfonylaldoimines with Methyl Isocyanoacetate Catalyzed by Gold (I)" Tetrahedron Lett. 37. 4969-4972 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yasuhiro uozumi, Hirokazu Kyota, Eiji Kishi, Kenji Kitayama, and Tamio Hayashi: "Homochiral 2,2'-Bis (oxazolyl)-1, binaphthyls as Ligands for Copper(I)-Catalyzed Asymmetric Cyclopropanation" Tetrahedron Asymmetry. 7. 1603-1606 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Tamio Hayashi, Motoi kawatsura, Hiroshi Iwamura, Yousuke Yamaura, and Yasuhiro Uozumi: "Catalytic Asymmetric Synthesis of Optically Active Olefins by Palladium-Catalysed Asymmetric Reduction of Racemic Allylic Esters with Formic Acid" Chem.Commun.1767-1768 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Tamio Hayashi, Motoi Kawatsura, and YAsuhiro Uozumi: "Regio-and Enantioselective Allylic Alkylation Catalysed by a Chiral Monophosphine-Palladium Complex" Chem.Commun.561-562 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi, Kazuhiko Kato, and Tamio Hayashi: "Catalytic Asymmetric Wacker-Type Cyclization" J.Am.Chem.Soc.119. 5063-5064 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Motoi Kawatsura, Yasuhiro Uozumi, and Tamio Hayashi: "Regiocontrol in Palladium-Catalysed Allylic Alkylation by Addition of Lithium Iodide" Chem.Commun.217 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Tamio Hatashi, Motoi Kawatsura, and Yasuhiro Uozumi: "Retention of Regiochemistry of Allylic Esters in Palladium-Catalyzed Allylic Alkylation in the Presence of a MOP Ligand" J.Am.Chem.Soc.210. XXXXXX (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi, Kazuhiko Kato, and Tamio Hayashi: "Asymmetric aza-Claizen Rearrangement of Allyl Imidates Catalyzed by Homochiral Cationic Palladium (II) complexes" Tetrahedron Asymmetry. 9. XXXXXX (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Rui Liang Lin Yan, Jennifer Loebach, Min Ge, Yasuhiro Uozumi, Klara Sekanina, Jeff Gildersleeve, Chris Thompson, Andri Smith, Kaustav Biswas, W.Clark Still, and Daniel Kahne: "Parallel Synthesis and Screening of a Solid Phase Carbohydrate Library" Science. 274. 1520-1522 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi, Hiroshi Danjo, and Tamio Hayashi: "New Amphiphilic Palladium-Phosphine Complexes Bound to Solid Supports : Preparation and Use for Pd-Catalyzed Allylic Substitution in Aqueous Media" Tetrahedron Lett. 38. 3557-3560 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 林 民生: "Regio-and Enantioselective Allylic Alkylation Catalyzed by Chiral Monophosphine-Palladium Compliexes" Chem.Commun.561-562 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 魚住 泰広: "Catalytic Asymmetric Wacker-Type Cyclization" J.Am.Chem.Soc.119. 5063-5064 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 魚住 泰広: "New Amphiphilic Palladium-Phosphine Complexes Bound to Solid Supports:Preparation and Use for Catalytic Allylic Substitution in Aqueous Media" Tetrahedron Lett.38. 3557-3560 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 林 民生: "Retention of Regiochemistry of Allylic Esters in Palladium-Catalyzed Allylic Alkylation in the Presence of MOP Ligand" J.Am.Chem.Soc.(in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] 川面 基: "Regiocontrol in Palladium-Catalysed Allylic Alkylation by Addition of Lithium Iodide" Chem.Commun.(in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] 魚住 泰広: "Asymmetric Aza-Claisen Rearrangement of Allyl Imidates Catalyzed by Homochiral Palladium (II) Complexes" Tetrahedron Asymmetry. (in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] 神川 卓: "Enantioposition-Selective Alkynylation of Biaryl Ditriflates by Palladium-Catalyzed Asymmetric Cross-Coupling" Tetrahedron Lett.37. 3161-3164 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 北山健司: "Asymmetric Hydrosilylation of Cyclic 1,3-Dienes Catalyzed by an Axially Chiral Monophosphine-Palladium Complex" Tetrahedron Lett.37. 4169-4172 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 魚住泰広: "Homochiral 2,2′-Bis(oxazolyl)-1,1′-binaphthyls as Chiral Ligands for Copper(I)-Catalyzed Asymmetric Cyclopropanation" Tetrahedron Asymmetry. 7. 1603-1606 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 林 民生: "Catalytic Asymmetric Synthesis of Optically Active Olefins by Palladium-Catalysed Asymmetric Reduction of Racemic Allylic Esters with Formic Acid" Chem.Commun.1767-1768 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 林 民生: "Regio-and Enantioselective Allylic Alkylation Catalyzed by Chiral Monophosphine-Palladium Complexes" Chem.Commun.(in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] 魚住泰広: "Catalytic Asymmetric Wacker-Type Cyclization" J.Am.Chem.Soc.(in press).

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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