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単一金属系新反応

Research Project

Project/Area Number 09238103
Research Category

Grant-in-Aid for Scientific Research on Priority Areas (A)

Allocation TypeSingle-year Grants
Research InstitutionOsaka University

Principal Investigator

村井 真二  大阪大学, 大学院・工学研究科, 教授 (00029050)

Co-Investigator(Kenkyū-buntansha) 真島 和志  大阪大学, 大学院・基礎工学研究科, 助教授 (70159143)
直田 健  大阪大学, 基礎工学研究科, 助教授 (20164113)
澤村 正也  東京大学, 大学院・理学系研究科, 助教授 (40202105)
溝部 裕司  東京大学, 生産技術研究所, 助教授 (40175609)
水野 一彦  大阪府立大学, 工学部, 教授 (10109879)
光藤 武明  京都大学, 大学院・工学研究科, 教授 (90026344)
村上 正浩  京都大学, 大学院・工学研究科, 助教授 (20174279)
岩澤 康裕  東京大学, 大学院・理学系研究科, 教授 (40018015)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥148,000,000 (Direct Cost: ¥148,000,000)
Fiscal Year 1999: ¥56,600,000 (Direct Cost: ¥56,600,000)
Fiscal Year 1998: ¥61,200,000 (Direct Cost: ¥61,200,000)
Fiscal Year 1997: ¥30,200,000 (Direct Cost: ¥30,200,000)
Keywords新反応 / 新概念 / 遷移金属元素 / 炭素共有結合 / 有機化合物 / 新現象 / 触媒反応 / React IR / 単一金属系 / 典型金属元素 / 有機合成 / 触媒 / NMR / 遷移金属 / 典型元素 / DNA
Research Abstract

当初から述べているように、本研究では単一金属系新反応の分野における新概念の開拓と蓄積をはかり、合成化学的応用に結びつけることを目的としている。これらの単一金属としては遷移金属元素や前周期遷移金属元素を主にとりあげ、典型金属元素もとりあげている。
本年度も引き続き、炭素共有結合形成のための新手法の開発を行った。そのため、遷移金属元素を中心として、これらと種々の型式の有機化合物ないし、有機化合物中の官能基との相互作用を極めて広範囲に調査し、これらを通じて得られる異常現象、非古典的現象の芽を蓄積し、専門の異なる研究者がチームをつくりつつ、これらの新現象の普遍化への方策を開拓した。
研究成果の一例として、前年度に導入した高性能な核磁気共鳴吸収装置は、引き続き順調に稼働しており、C-H/オレフィンカップリング反応機構をさらに深く追及していくことができた(村井)。14族有機金属化合物の光誘起電子移動反応の新たな解明にむけての成果が得られた(水野)。また、炭素間単結合間に分子内のオレフィンが挿入するという新触媒反応を見い出した(村上)。
さらに、本年度導入した反応解析モニタリングシステム(React IR 1000)は順調に稼働しており、反応の機構や経路についての重要なデータを鋭意蓄積しつつある(澤村)。
全体として、本年度は計画通り順調に研究が進展したといえる。

Report

(3 results)
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] N. Chatani, Y. Ie, F. Kakiuchi, S. Murai: "Ru3(CO)12-Catalyzed Decarbonylative Cleavage of a C-C Bond of Alkyl Phenyl Ketones"J. Am. Chem. Soc.. 121. 8645-8646 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Isobe, A. Obayashi, M. Sawamura, E. Nakamura: "A Cage with Fullerene End Caps"J. Am. Chem. Soc. (in press). 122.

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Mashima, Y. Matsuo, K. Tani: "Unique Complexation of 1, 4-Diaza-1, 3-butadiene Ligand on Half-metallocene Fragments of Niobium and Tantalum"Organometallics. 18. 1471-1481 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Seino, C. Arita, D. Nonokawa, G. Nakamura, Y. Mizobe, M. Hidai: "Conversion of Benzaldehyde Imines into Isocyanides at a Low-Valent Molybdenum Center Preparation and Reactivities of Isocyanide-Dinitrogen Complexes ..."Organometallics. 18. 4165-4173 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Suzuki, K. Iida,K. Wada, T. Kondo, T. Mitsudo: "Catalytic Oxidation of pentacyclo [6.6.0.0 2,6.03,13.010,14] tetradeca-4, 11-diene Syntheses of Novel Polyfunctional Half-Open Cage Compounds"Tetrahediron Lett.. 40. 2997-3000 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Murakami, K. Itami, Y. Ito: "Construction of Eignt-Membered Carbocycles by Palladium-Catalyzed [4+4] Cycloaddition of Vinylallenes"Synlett. 951-953 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Fujii,F.Kakiuchi,A.Yamada,N.Chatani,S.Murai: "Transition-Metal-Catalyzed Intramolecular Cyclization of 1,5-and 1,6-Dienes via Direct Cleavage and Addition of the Carbon-Hydrogen Bond." Bull.Chem.Soc.Jpn.71. 285-298 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Sato,F.Kakiuchi,N.Chatani,S.Murai: "Ruthenium-Catalyzed Reactions of Acyclic a,b-Enones with Olefins and Their Reaction Mechanisms." Chem.Lett.893-894 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Takaya,T.Naota,S-I.Murahashi: "Irdium Hydride Complex Catalyzed Addtion of Nitriles to Carbon-Nitrogen Triple Bonds of Nitriles." J.Am.Chem.Soc.120. 4244-4245 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Mashima,Y.Nakayama,J.G.Hamilton,J.J.Rooney: "Control of Stereoselectivity in the Ring-Opening Metathesis Polymerization of Norbornene by the Auxiliary Ligands,Butadiene and o-Xylylene,in・・・" Organometallics. 17. 4183-4195 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Mashima,T.Oshiki,and K.Tani,: "The First Oxidative Addition of a Hypervalent Compound to Metallic Lanthanoid: Synthesis, Characterization,and Reaction of Samarium(II)Bistrifluoromethanesulfonate Derived from・・・" J.Org.Chem.63. 7114-7116 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Tamai,N.Ichinose,T.Tanaka,T.Sasuga,I.Hashida,K.Mizuno: "Generation of Polyphenylene(PP)Radical Cations and Cosensitization of PP in the 9,10-Dicyanoanthracene-Sensitized Photochemical Chain Reactions of 1,2-Bis(4-methoxyphenyl)cyclopropane." J.Org.Chem.63. 3204-3212 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] G.Nakamura,Y.Harada,C.Arita,H.Seino,Y.Mizobe,M.Hidai: "Unprecedented Conversion of Benzylideneanilines into Phenyl Isocyanides Promoted by a Low-Valent Molybdenum Complex." Organometallics. 17. 1010-1012 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Mizobe,M.Hosomizu,M.Hidai: "Syntheses of Ruthenium Hydridotris(1-pyrazolyl)borate Complexes Having Sulfur Donor Coligand." Inorg.Chim.Acta.273. 238-243 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Kondo,K.Kodoi,E.Nishinaga,T.Okada,Y.Morisaki,T.Mitsudo: "Ruthenium-Catalyzed β-Allyl Elimination Leading to Selective Cleavage of a Carbon-Carbon Bond in Homoally Alcohols." J.Am.Chem.Soc.120. 5587-5588 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Kondo,N.Hiraishi,T.Morisaki,K.Wada,Y.Watanabe,T.Mitsudo: "First Intermolecular Hydroacylation of 1,3-Dienes with Aldehydes Catalyzed by Ruthenium." Organometallics. 17. 2131-2134 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Murakami,T.Itahashi,H.Amii,K.Takahashi,Y.Ito: "New Domino Sequences Involving Successive Cleavage of Carbon-Carbon and Carbon-Oxygen Bonds: Discrete Product Selection Dictated by Catalyst Ligands." J.Am.Chem.Soc.120. 9949-9950 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Murakami,K.Itami,M.Ubukata,I.Tsuji,Y.Ito: "Iridium-Catalyzed[5+1]Cycloaddition: Allenylcyclopropane as a Five-Carbon Assembling Unit." J.Org.Chem.63. 4-5 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Murai, N.Chatani, F.Kakiuchi: "Catalytic Addition of C-H Bonds to Multiple Bonds." Pure Appl.Chem.69. 589-594 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Fujii, F.Kakiuchi, A.Yamada, N.Chatani, S.Murai: "Asymmetric Intramolecular C-H/Olefin Coupling : Asymmetric Cyclization Reactions of 1,5-Dienes Catalyzed by Rhodium Complexes." Chem.Lett.425-426 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Kozlov, K.Asakura, Y.Iwasawa: "Bis (2-pyridinecarboxylato) vanadium (IV) in NaY Zeolite Cages : Synthesis and Spectroscopic Properties." Chem.Lett.313-314 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Iwasawa: "Surface Catalytic Reactions Assisted by Gas Phase Molecules." Acc.Chem.30. 103-109 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Naota, H.Takaya, S.Murahashi: "Ruthenium-Catalyzed Reactions for Organic Synthesis." Chem.Rev. (in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Takaya, T.Naota, S.Murahashi: "Iridium Hydride Complex Catalyzed Addition of Nitriles to Carbon-Nitrogen Triple Bonds of Nitriles." J.Am.Chem.Soc.(in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Mashima, S.Kaneko, K.Tani: "A 16 Electron Cyclobutadiene-benzene-1,2-dithiolate Complex of Palladium (II) Bearing A Two-legged Pianostool Geometry : (η^4-C_4Me_2(^tBu)_2)Pd(1,2-S_2C_6H_4)." Chem.Lett.16. 347-348 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Mashima, M.Tanaka, K.Tani, A.Nakamura, W.Mori, K.Yamaguchi: "Elongation of the Quadruple Cr-Cr Bond Induced by Two PtMe Moieties in the Linearly Aligned Tetrametal System,PtMe_2・・・Cr-Cr・・・PtMe_2." J.Am.Chem.Soc.119. 4307-4308 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Kondo, N.Suzuki, T.Okada, T.Mitsudo: "First Ruthenium-Catalyzed Intramolecular Pauson-Khand Reaction." J.Am.Chem.Soc.119. 6187-6188 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Fujita, K.Ito, T.Kondo, T.Mitsudo: "Reaction of a (π-Vinylcarbene) iron Complex with Tricarbonyl (η^41,5-cyclooctadiene) ruthenium. Preparation,Structure,and Reactivity of Novel (μ-Vinylcarbene) (Fe-Ru) Complexes." Organometallics. 16. 677-681 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Murakami, K.Takahashi, H.Amii, Y.Ito: "Rhodium (I)-Catalyzed Successive Double Cleavage of Carbon-Carbon Bonds of Strained Spiro Cyclobutanones." J.Am.Chem.Soc.119. 9307-9308 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Murakami, K.Itami, M.Ubukata, I.Tsuji, Y.Ito: "Iridium-Catalyzed [5+1] Cycloaddition : Allenylcyclopropane as a Five-Carbon Assembling Unit." J.Org.Chem.63. 4-5 (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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