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Reactive Organometallics

Research Project

Project/Area Number 05236105
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionOsaka University

Principal Investigator

MURAHASHI Shun-ichi  Osaka University, Graduate School of Engineering Science, Professor, 基礎工学部, 教授 (60029436)

Co-Investigator(Kenkyū-buntansha) YAMAMOTO Yoshinori  Graduate School of Science, Tohoku University, Professor, 大学院・理学研究科, 教授 (60029519)
OKAZAKI Renji  Graduate School of Science, The University of Tokyo, Professor, 大学院・理学系研究科, 教授 (70011567)
MORO-OKA Yoshihiko  Tokyo Institute of Technology, Research Laboratory of Resources Utilization, Pro, 資源化学研究所, 教授 (70016731)
YAMAMOTO Akio  Waseda University, School of Science and Engineering, Professor, 理工学部, 教授 (30016711)
NAGAKURA Saburo  Kanagawa Academy of Science and Technology, President, 理事長 (30013444)
Project Period (FY) 1993 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥126,300,000 (Direct Cost: ¥126,300,000)
Fiscal Year 1996: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1995: ¥11,900,000 (Direct Cost: ¥11,900,000)
Fiscal Year 1994: ¥47,400,000 (Direct Cost: ¥47,400,000)
Fiscal Year 1993: ¥64,000,000 (Direct Cost: ¥64,000,000)
KeywordsReactive Organometallics / Reactive Organometallics of Transition Metals / Reactive Organometallics of Non-transition Metals / Organometallics of Organic Active Intermediates / Catalysis of Reactive Organometallics / Molecular Recognition of Reactive Organometallics / 有機典型金属の創製
Research Abstract

Aiming to acquire innovative method of chemical transformation for the future, the present research project designed and produced reactive organometallics that suit appropriate purposes, and placed emphasis on clarifying their function of catalysis and molecular recognition and examining their possibility of working as functional materials. The following research groups were set up depending on the research theme :
A) Reactive Organometallics of Transition Metals (S.-I.Murahashi)
B) Reactive Organometallics of Non-transition Metals (R.Okazaki)
C) Organometallics of organic Active Intermediates (Y.Yamamoto)
D) Catalysis of Reactive Organometallics (A.Yamamoto)
E) Molecular Recognition of Reactive Organometallics (Y.Moro-oka)
110 researchers in total engaged in this project and in consequence, fruitful results that are original enough to promoto the introduction of the leading technology were obtained in the field of organometallic chemistry, organic synthesis, catalysis, and functional materials.
The meetings of head of research group and evaluation group were held twice a year (seven in total) to promote and to generalize the project. Open symposiums were held 7 times to exchange lively and meaningful opinions between researchers, and about 200 people including researchers and those from private enterprises from outside took part in every symposium. The gist of the symposium was published each time and was distributed to all concerned. In addition, we issued public relations bulletins 8 times and also filed a report on our three-year research "Reactive organometallics-Synthesis and Function- " in English and distributed it to the Ministry of Education, Science, Culture and Sports, and researchers at large to make our results widely known at home as well as abroad.

Report

(5 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (45 results)

All Other

All Publications (45 results)

  • [Publications] S.-I.Murahashi: "Ruthenium-Catalyzed Oxidation of Phenols with Alkyl Hydroperoxides.A Novel,Facile Route to 2-Substituted" J.Am.Chem.Soc.118. 2509-2510 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Okazaki: "The First Rotational Isomers of Stable Selenoaldehydes and Their 1-Tungsten Complex" Angew.Chem.,Int.Ed.Engl.35. 660-662 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Yamamoto: "A New Palladium Catalyzed Benzannulation of Conjugated Enynes" J.Am.Chem.Soc.118. 3970-3971 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Yamamoto: "Activation of C-O and C-N Bonds in Allylic Alcohols and Amines by Palladium Complexes Promoted by CO_2" Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Moro-oka: "Deoxygenative Reduction of Diruthenium Carbonyl Complexes(^5-C_5H_4R)_2Ru_2(-CH_2)_n(-CO)_<2-n>(CO)_2(n=1,2;R=H,Me)" Organometallics. 15. 2548-2553 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.-I.Murahashi, T.Naota, N.Miyaguchi, S.Noda: "Ruthenium-Catalyzed Oxidation of Phenols with Alkyl Hydroperoxides. A Novel Facile Route to 2-Substituted Quinones" J.Am.Chem.Soc.118. 2509-2510 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Takeda, N.Tokitoh, R.Okazaki: "The First Rotational Isomers of Stable Selenoaldehydes and Their 1-Tungsten Complex" Angew.Chem., Int.Ed.Engl.35. 660-662 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Saito, M.M.Salter, V.Gevorgyan, N.Tsuboya, K.Tando, Y.Yamamoto: "A New Palladium Catalyzed Benzannulation of Conjugated Enynes" J.Am.Chem.Soc.118. 3970-3971 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Sakamoto, I.Shimizu, A.Yamamoto: "Activation of C-O and C-N Bonds in Allylic Alcohols and Amines by Palladium Complexes Promoted by CO_2. Synthetic Application to Allylation of Nucleophiles, Carbonylation, and Allylamine Disproportionation" Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Akita, R.Hua, T.Oku, Y.Moro-oka: "Deoxygenative Reduction of Diruthenium Carbonyl Complexes (eta^5-C_5H_4R)_2-Ru_2 (mu-CO) (CO)_2 with Hydrosilanes Leading to Bridging Methylene Complexes (eta^5-C_5H_4R)_2Ru_2 (mu-CH_2)_n (mu-CO)_<2-n> (CO)_2 (n=1,2 ; R=H,CH_3)" Organometallics. 15. 2548-2553 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.-I.Murahashi: "Ruthenium-Catalyzed Oxidation of Phenols with Alkyl Hydroper-Oxides.A Novel,Facile Route to 2-Substituted Quinones" J.Am.Chem.Soc.118. 2509-2510 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] R.Okazaki: "The First Rotational Isomers of Stable Selenoaldehydes and Their 1-Tungsten Complex" Angew.Chem.,Int.Ed.Engl.35. 660-662 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Yamamoto: "A New Palladium Catalyzed Benzannulation of Conjugated Enynes" J.Am.Chem.Soc.118. 3970-3971 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] A.Yamamoto: "Activation of C-O and C-N Bonds in Allylic Alcohols and Amines by Palladium Complexes Promoted by CO_2." Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Moro-oka: "Deoxygenative Reduction of Diruthenium Carbonyl Complexes(η^5-C_5H_4R)_2Ru_2(μ-CH_2)_n(μ-CO)_<2-n>(CO)_2(n=1,2;R=H,CH_3)" Organometallics. 15. 2548-2553 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Murahashi,Shun-Ichi: "Ruthenium-Catalyzed Aldol and Michael Reactions of Nitriles" J. Am. Chem. Soc.117. 12436-12451 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Murahashi,Shun-Ichi: "Palladium(II)-Catalyzed Asymmetric Acetalization of Alkenes" J. Org. Chem.60. 6159-6167 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Okazaki,Renji: "The first Pb-containing cyclic polysulfides..." Organometallics. 14. 3121-3123 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Okazaki,Renji: "Synthesis, Structure, and Thermolysis of a Tetracoordinate..." J. Am. Chem. Soc.117. 6142-6143 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yamamoto,Yoshinori: "Synthesis of Netropsin and Distamycin Analogue Bearing.." J. Org. Chem.60. 3352-3357 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yamamoto,Yoshinori: "Most Stable Conformer of 2-Phenylpropanal Elucidated by.." J. Am. Chem. Soc.117. 3167-3170 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yamamoto,Akio: "Synthesis and Properties of Cationic Organopalladium Complexes" Bull. Chem. Soc. Jpn.68. 654-660 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yamamoto,Akio: "Palladium-Catalyzed Double and Single Carbonylation" Bull. Chem. Soc. Jpn.68. 433-446 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Moro-oka,Yoshihiko: "1,2-H Shift on Tetranuclear Ethynyl Complexes" Organometallics. 14. 2775-2780 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Moro-oka,Yoshihiko: "Deoxygenative Reduction of Dimolybdenum Carbonyl Complexes" Organometallics. 14. 5209-5220 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Murahashi,Shun-Ichi: "Copper(I)-Catalyzed Amination of Propargyl Esters. Selective Synthesis of Propargylamines,1-Alken-3-ylamines,and (Z)-..." The Journal of Organic Chemistry. 59. 2282-2284 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Murahashi,Shun-Ichi: "Tungstate-Catalyzed Decarboxylative Oxidation of N-Alkyl-α-amino Acids-An Efficient Method for Regioselective Synthesis of ...." The Journal of Organic Chemistry. 59. 6170-6172 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yamamoto,Akio: "Synthesis of the First Carbon Dioxide Coordinated Palladium(0)Complex,Pd(η^2-CO_2)(PMePh_2)_2" Organometallics. 13. 407-409 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yamamoto,Akio: "Synthesis and Thermolysis Behavior of Monoethylpalladium Complexes,EtPd(X)(PMe_3)_2(X=Electronegative Ligands)" Organometallics. 13. 3517-3524 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Moro-oka,Yoshihiko: "A Monomeric Side-On Peroxo Manganese Complex:Mn(O_2)(3,5-iPr_2-pzH)(HB(3,5-iPr_2pz)_2)" Journal of the American Chemical Society. 116. 12079-12080 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Moro-oka,Yoshihiko: "Reaction of the Heterobimetallic Metal-substituted Vinylidene Complex,Cp'(CO)_2Mn(=C=C(H)-Fp^*),with Excess BuLi Giving..." Organometallics. 13. 2516-2520 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Okazaki,Renji: "Synthesis,Structure,and Thermolysis of a 1,5-Dioxa-4λ^5-phos-phaspiro[3.3]heptane:a Novel Pentacoordinate 1,2-Oxaheptane" Journal of the American Chemical Society. 116. 4509-4510 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Okazaki,Renji: "Synthesis and Structure of 2,4,6-Tris(bis(trimethylsilyl)methyl)thiobenzaldehyde:The First Isolation of Rotational Isomers..." Journal of the American Chemical Society. 116. 7907-7908 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yamamoto,Yoshinori: "Palladium Catalyzed Addition of Activated Methylene and Methyne Compounds to Allenes" Journal of the American Chemical Society. 116. 6019-6020 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yamamoto,Yoshinori: "Transition Metal Catalyzed Addition of Certain Nucleophiles to Imines" Journal of the American Chemical Society. 116. 3161-3162 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Murahashi,Shun-Ichi: "Palladium(0)-Catalyzed Alkoxycarbonylation of Allyl Phosphates and Acetates" The Journal of Organic Chemistry. 58. 1538-1545 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Murahashi,Shun-Ichi: "Ruthenium-Catalyzed Oxidative Transformation of Alkenes to α-Ketols with Peracetic Acid.Simple Synthesis of Cortisone Acetate." The Journal of Organic Chemistry. 58. 2929-2930 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yamamoto,Akio: "Preparation and properties of alkylpalladium(II) and -platinum(II)alkynyl complexes" Journal of Organometallic Chemistry. 452. 247-250 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yamamoto,Akio: "Synthesis,characterization,and carbonylation reactions of methylpalladium amide,carbamate,and alkyl carbonate complexes" Journal of Organometallic Chemistry. 451. 221-229 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Moro-oka,Yoshihiko: "A reaction mimic of tyrosine hydroxylase:hydroxylation of a phenoxo ferric complex to a catecholato complex with mCPBA" Journal of the American Chemical Society. 115. 9335-9336 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Moro-oka,Yoshihiko: "Formation of (μ-hydroxo)(μ-azido) dinuclear copper complexfrom μ-η^2:η^2-peroxo complex" Journal of the American Chemical Society. 115. 7874-7875 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Okazaki,Renji: "Synthesis and crystal structure of the first stable diarylgermanethione" Journal of the American Chemical Society. 115. 8855-8856 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Okazaki,Renji: "Synthesis,structure,and reactivity of extremely hindered disilenes:the first example of thermal dissociation of a disilene into a silylene" Journal of the American Chemical Society. 115. 10428-10429 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yamamoto,Yoshinori: "Mediation of the reactivity of the strong Lewis acid titaniumtetrachloride by complexation with XPh_3 (X=arsenic,antimony,bismuth)" The Journal of Organic Chemistry. 58. 4783-4784 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yamamoto,Yoshinori: "Syn-S_N2′ pathway in the reaction of certain γ-(mesyloxy)α,β-enoates with RCu(CN)-MgX・BF_3 reagents.Importance of MgX and bulky R group upon the diastereoselectivity" The Journal of Organic Chemistry. 58. 1207-1214 (1993)

    • Related Report
      1993 Annual Research Report

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

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