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Development of Novel Catalyst System for Highly Enantioselective Hydroformylations and Its Application for the Syntheses of Biologically Active Compounds.

Research Project

Project/Area Number 06555272
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

NOZAKI Kyoko (1995)  Kyoto univ., Graduate School of Engineering, Instructor, 工学研究科, 助手 (60222197)

高谷 秀正 (1994)  京都大学, 工学部, 教授 (40022644)

Co-Investigator(Kenkyū-buntansha) HAGIWARA Isao  Mitsubishi Gas Chem.Coap., Tokyo Lab., Sub Chief Research Chemist, 東京研究所, 副主任研究員
TOMITA Tetsuro  Mitsubishi Gas Chem.Coap., Tokyo Lab., Research Director, 東京研究所, 主任研究員
SAYO Noboru  Takasago International Coap., Fine Chem.Division, Research Director, ファインケミカル研究所, 第一主幹
KUMOBAYASHI Hidenori  Takasago International Coap., Fine Chem.Division, Director, ファインケミカル研究所, 所長
OHTA Tetsuo  Doshisya Univ., Fac.of Engin., Associate Professor, 工学部, 助教授 (50213731)
野崎 京子  京都大学, 工学部, 助手 (60222197)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥10,300,000 (Direct Cost: ¥10,300,000)
Fiscal Year 1995: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1994: ¥9,000,000 (Direct Cost: ¥9,000,000)
KeywordsOlefin / Carbon monoxide / Hydroformylation / Copolymerization / Optically active aldehyde / Sulfur-containing olefins / Conjugated diene / Phosphine-phosphite / 不斉接触反応 / ロジウム / 不斉ヒドロホルミル化 / BINAPHOS / β-ラクタム
Research Abstract

(1) Asymmetric hydroformylation of sulfur-containing olefins, such as vinyl-and allyl-sulfide, sulfoxide, sulfones has been performed in high enantioselectivities by using a rhodium complex of chiral phosphine-phosphite, (R,S) -BINAPHOS.The resulting oxo-aldehydes have potential use as synthetic intermediates for various biologically active compounds.
(2) Asymmetric hydroformylation of conjugated dienes have also been examined. There are four carbons in the dienes which are capable to be attached to the formyl group. For various diences, the present system chooses one of the four possibilities, in high enantioselectivities.
(3) Highly enantioselective copolymerization of propene and carbon monoxide has been performed by using Pd (II) - (R,S) -BINAPHOS.The catalyst system produces poly (alt-propene-CD) of the highest molecular weight as well as in the highest enantioselectivity ever reported. The reaction mechanism was also investigated by NMR studies.

Report

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

    (20 results)

All Other

All Publications (20 results)

  • [Publications] N. Sakai: "Asymmetric Hydroformylation of 1,2-Disubstituted Olefins Catalyzed by Chiral Phosphinephosphite-Rh(I)Complexes." J. Chem. Soc., Chem. Commun.395-396 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T. Horiuchi: "Synthesis of (R)-and (S)-7,'7-Bis(diphenylphosphino)-2,2'-dimethoxy-1,1'-binaphthyl,a New Axially Dissymme-tric Bis(triarylphosphine)." Tetrahedron: Asymmetry. 5. 325-328 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T. Higashijima: "Synthesis of New Chiral Phosphinephosphites Having 2-Diphenylphosphinobiphenyl-2'-yl Backborne and Their Use in Rh(I)-Catalyzed Asymmetric Hydroformylations." Tetrahedron Lett.35. 2023-2026 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Nozaki: "Acylcyanation of Terminal Acetylenes. Palladium-Catalyzed Addition of Aryloyl Cyanides to Arylacety-lenes." J. Org. Chem.59. 2679-2681 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Nozaki: "Highly Enantioselective Alternating Copolymerization of Propene with Carbon Monoxide Catalyzed by a Chiral Phosphine-phosphite-Pd(II)Complex." J. Am. Chem. Soc.117. 9911-9912 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T. Nanno: "Asymmetric Hydroformylation of Sulfur-Containing Olefins Catalyzed by BINAPHOS-Rh(I)Complexes." Tetrahedron: Asymmetry. 6. 2583-2591 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T. Horiuchi: "Asymmetric Hydroformylation of Conjugated Dienes Catalyzed by[(R)-2-diphenylphosphiono-l'l-dinaphtha-len-2'-yl][(S)-l,l'-dinaphthalem-2,2'-diyl]phosphite-rhodium(I)." Chem. Commun. 155-156 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] N.Sakai: "Asymmetric Hydroformylation of 1,2-Disubstituted Olefins Catalyzed by Chiral Phosphinephosphite-Rh (I) Complexes." J.Chem.Soc., Chem.Commun.395-396 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Horiuchi: "Synthesis of (R) -and (S) -7,7'-Bis (diphenylphosphino) -2,2'-dimethoxy-1,1'-binaphthyl, a New Axially Dissymmetric Bis (triarylphosphine)." Tetrahedron : Asymmetry. 5. 325-328 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Higashijima: "Synthesis of New Chiral Phosphinephosphites Having 2-Diphenylphosphinobiphenyl-2'-yl Backborne and Their Use in Ph (I) -Catalyzed Asymmetric Hydroformylations." Tetrahedron Lett.35. 2023-2026 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Nozaki: "Acylcyanation of Terminal Acetylenes. Palladium-Catalyzed Addition of Aryloyl Cyanides to Arylacetylenes." J.Org.Chem.59. 2679-2681 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Nozaki: "Highly Enantiosalective Alternating Copolymerization of Propene with Carbon Monoxide Catalyzed by a Chiral Phosphine-phosphite-Pd (II) Complex." J.Am.Chem.Soc.117. 9911-9912 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Nanno: "Asymmetric Hydroformylation of Sulfur-Containing Olefins Catalyzed by BINAPHOS-Rh (I) Complexes." Tetrahedron : Asymmetry. 6. 2583-2591 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Horiuchi: "Asymmetric Hydroformylation of Conjugated Dienes Catalyzed by [ (R) -2-diphenylphosphiono-1,1'-dinaphthalen-2'-yl] [ (S) -1.1'-dinaphthalem-2,2'-diyl] phosphite-rhodium (I)." Chem.Commun. 155-156 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Nozaki: "A Chiral Bimctallic Lewis Acid:A Coopcrative Binding of Two Amine Molecules to a Chiral Diboronic Ester" Anyew.Chem.,Int.Ed.Engl.33. 2452-2454 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Nozaki.: "Acylcyanation of Terminal Acetylenes:Palladium Catalyzcd Addition of Aryloyl Cyanides to Arylacetylenes" J.Org.Chem.59. 2679-2681 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Takaya: "Cationic BINAP-Ru(II)Halide Complexes:Highly Efficient Calalysts for Stereoselective Asymmetric Hydrogenation of α- and β-Functionalized Ketones" J.Org.Chem.59. 3064-3076 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Takaya: "Enantioselcetive Hydrogenation of Acyclic Aromatic Ketones Catalyzed by BINAP-Ir(I)-Aminophosphine Systems" Tetrahedron:Asymmitry. 5. 1179-1182 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Takaya: "Facile Introduction of Michael Acceptors into Nitrogen Heterocycles.A New Efficient Route to Fused α-Methylene-γ-lactams" Chem.Lett.1809-1812 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Takaya: "Highly Enantioselective Hydrogenation of α,β-Unsaturated Carboxylic Acids Catalyzed by H_8-BINAP-Ru(II)Complexes" Synlett. 501-503 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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