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New Development of Electron Transfer in Co-ordination Compounds

Research Project

Project/Area Number 05235106
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionKyoto University

Principal Investigator

UTIMOTO Kiitiro  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (90025958)

Co-Investigator(Kenkyū-buntansha) HISAEDA Yoshio  Kyushu University, Faculty of Engineering, Professor, 工学部, 教授 (70150498)
TOKUDA Masao  Hokkaido University, Faculty of Engineering, Professor, 工学部, 教授 (80001296)
FUJISAWA Kiyoshi  Tokyo Institute of Technology, Research Laboratory of Resources Utilization, Ins, 資源化学研究所, 助手 (10251670)
AIZAWA Masuo  Tokyo Institute of Technology, Department of Bioengineering, Professor, 生命理工学部, 教授 (00016742)
久枝 良雄  九州大学, 工学部, 教授 (79777251)
横野 照尚  九州大学, 工学部, 助教授 (10203887)
北島 信正  東京工業大学, 資源化学研, 助教授 (20177843)
碇山 義人  東京工業大学, 生命理工学部, 助教授 (10202847)
Project Period (FY) 1993 – 1995
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥69,200,000 (Direct Cost: ¥69,200,000)
Fiscal Year 1995: ¥20,700,000 (Direct Cost: ¥20,700,000)
Fiscal Year 1994: ¥21,900,000 (Direct Cost: ¥21,900,000)
Fiscal Year 1993: ¥26,600,000 (Direct Cost: ¥26,600,000)
KeywordsELECTRON TRANSFER / STEREOSELECTIVE / DIMETALLIC REAGENT / ORGANOZINC COMPOUND / LEAD CATALYST / VITAMIN B_<12> / COORDINATION COMPOUND / BIOSENSING / 有機金属錯体 / ジメタル活性種 / 異種金属相互作用 / アルキリデン化反応 / ポリフィリン錯体 / 分子認識 / 有機電気化学 / 金属錯体 / 生物有機化学 / 反応性電極 / 高選択的有機合成反応 / 有機金属 / 電気化学 / 電解
Research Abstract

Investigators of this group extended the research on electron transfer processes in transition metal coordination compounds and combination of organic compounds and metal or low-valent metal salts. These research are fundamentally important in organic electrochemistry, electrobiochemistry, organic chemistry, biochemistry, and organic synthesis. In the period of this Scientific Research on Priority Areas of Organic Electrochemistry, the investigators of the group produced the followihg results.
1.Studies on Electron Transfer Process and Use of Generated Reactive Species : Electron transfer from metal to organic compounds in an elemental process in organic electrochemistry. Two reactions related to controlled electron transfer from metal to organic halides have been developed. One is stereocontrolled reaction containing enantioselective generation of chiral building block from 1,1-dihaloalkanes in the presence of chiral aldehydes. This novel process would provide new asymmetric synthesis … More of various organic compounds. Second one is selective electron transfer to dihalides from metal mediated or catalyzed by another metal. Diiodomethane reacted with pure zinc to give iodomethylzinc iodide in excellent yield ; formation of dimetallic species, bis (iodozincio) methane, could not be detected. In contrast to the reaction using pure zinc, treatment of diiodomethane with zinc containing catalytic amount of lead afforded bis (iodozincio) methane exclusively. Formation of bis (iodozincio) methane from iodomethylzinc iodide by treatment with zinc containing lead or a mixture of pure zinc and catalytic amount of PbCl_2 suggested that electron transfer to iodomethylzinc iodide was controlled by lead catalyst.
2.Construction of New Electron Transfer System : New electron transfer systems have been extensively studies in order to develop highly selective reactions using reactive species generated by selective electron transfer and diastereoselective transfer of organic moieties from coordination compounds to substrates. Some successful results were obtained using modified Vitamin B_<12>.
3.Electron Transfer Process in Biochemical Interaction : Electrochemical luminescence probing of biological activities have been extensively studied. DNA-interfacing antitumor and antiviral agents were characterized by using this process. Antibody recognition was also studied by applying the method. Less

Report

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

    (34 results)

All Other

All Publications (34 results)

  • [Publications] MATSUBARA,S.;YOSHIOKA,M.;UTIMOTO,K.: "Samarium-Mediated Highly Stereoselective Reaction of 1,1-Dihaloalkanes with Aldehydes.Generation of Chiral α-Iodoalkyl Building Block from Achiral 1,1-Diiodoethane" Angew.Chem.Intern.Ed.Engl.37. (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] UTIMOTO,K.;TAKAI,T.;MATSUI,T.;MATSUBARA,S.: "Ethyl d-Diiodosamario-β-oxobutanoates,Generation by the Reaction of Ethyl Bromoacetate with Samarium Diiodide and Synthetic Applications" Bull.Soc.Chim.Fr.(1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] OHNO,T.;OGAWA,A.;HISAEDA,Y.;MURAKAMI,Y.: "Isomerization of an Axail Ligand Coordinated to Hydrophobic Vitamin B_<12> as Effected by Cyanide Ion and Microenvironment" Tetrahedron Lett.35. 9589-9592 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] TOKUDA,M.;KURONO,N.;MIMURA,N.: "New Electrochemical Preparation of Reactive Zinc with Large Surface Area" Chem.Lett.1091-1092 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] OSAWA,M.;TANAKA,M.;FUJISAWA,K.;KITAJIMA,N.;MORO-OKA,Y.: "A Monomeric Zinc Complex Ligated by an Unsymmetric Hydrotris(Pyrazolyl)borate Containg an OH Group" Chem.Lett.397-398 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] AIZAWA,M.: "Electrochemically Gnerated Luminescence of Luminol and Its Application for Biosensing" Proceedings of 2nd International Symposium on Electroorganic Synthesis,Kurashiki. 419-424 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] MATSUBARA,S. ; YOSHIOKA,M, ; UTIMOTO,K.: "Samarium-Mediated Highly Stereoselective Reaction of 1,1-Dihaloalkanes with Aldehydes. Generation of Chiral alpha-Iodoalkyl Building Block from Achiral 1,1-Diiodoethane" Angew.Chem.Intern.Ed.Engl.37. 0000 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] UTIMOTO,K. ; TAKAI,T. ; MATSUI,T. ; MATSUBARA,S.: "Ethyl d-Diiodosamario-beta-oxobutanoates, Generation by the Reaction of Ethyl Bromoacetate with Samarium Diiodide and Synthetic Applications" Bull.Soc.Chem.Fr.0000 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] MATSUBARA,S. ; HORIUCHI,M. ; TAKAI,K. ; UTIMOTO,K.: "Alkylidenation of Ketones by gem-Dibromoalkane, SmI_2, and Sm in the Presence of Catalytic Amount of CrCl_3" Chem.Lett.259 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] OHNO,T. ; OGAWA,A. ; HISAEDA,Y. ; MURAKAMI,Y.: "Isomerization of an Axial Ligand Coordinated by Hydrophobic Vitamin B_<12> as Effected by Cyanide Ion and Microenvironment" Tetrahedron Lett.35. 9589 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] TOKUDA,M. ; KURONO,N. ; MIMURA,N.: "New Electrochemical Preparation of Reactive Zinc with a Large Surface Area" Chem.Lett.1091 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] TOKUDA,M. ; KABUKI,T. ; KATOH,Y. ; SUGINOME,H.: "Regioselective Synthesis of beta, gamma-Unsaturated Acids by the Electrochemical Carboxylation of Allylic Bromides Using a Reactive-metal Anode" Tetrahedron Lett.36. 3345 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] TOKUDA,M. ; KABUKI,T. ; YOSHIKAWA,M. ; TOKUHASHI,T. ; MIYAZAWA,M, ; ORITO,K. ; SUGINOME,H.: "Syntesis of Unsaturated Lactones Utilizing Electrochemical Carboxtlation" Proceedings of 2nd International Symposium on Electroorganic Synthesis, Kurashiki. 257 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] OSAWA,M. ; TANAKA,M. ; FUJISAWA,K. ; KITAJIMA,N. ; MORO-OKA,Y.: "A Monomeric Zinc Complex Ligated by an Unsymmetric Hydrotris (pyrazolyl) borate Containing an OH Group" Chem.Lett. 397 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] FUJISAWA,K. ; TANAKA,M. ; MORO-OKA,Y. ; KITAJIMA,N.: "A Monomeric Side-On Superoxocopper (II) Complex : Cu (O_2) (HB (3-tBu-5-iPrpz)_3)" J.Am.Chem.Soc.116. 12079 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] AIZAWA,M.: "Electrochemically Generated Luminescence of Luminol and Its Application for Biosensing" Proceedings of 2nd International Symposium on Electroorganic Synthesis, Kurashiki. 419 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 内本喜一朗: "Alkylidenation of Ketones by gem-Dibromoalkane,SmI_2,and Sm in the Presence of Catalytic Amount of CrCl_3" Chem.Lett.259-260 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 内本喜一朗: "Formal Hydroallylation of Carbon-Carbon Triple Bonds via Tantalum-Alkyne Complexes.Stereoselective Preparation of 1,4-Dienes" Chem.Lett.315-316 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 内本喜一朗: "Diastereoselective 1,4-Addition of Organocopper-Lanthanoid Reagents to α,β-Unsaturated Ketones Containing 1,3-Oxathiane as a Chiral Auxiliary" Synlett.501-502 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 徳田昌生: "Regioselective Synthesis of β,γ-Unsaturated Acid by the Electorochemical Carboxylation of Allylic Bromides Using a Reactive-metal Anode" Tetrahedron Lett.36. 3345-3348 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 久枝良雄: "Isomerization of an Axial Ligand Coordinated to Hydrophobic Vitamin B_<12> as Effected by Cyanide Ion and Microenvironment" Tetrahedron Lett.36. 9589-9592 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 相澤益男: "Biosensing of Benzene Derivatives in the Enviroment by Luminescent Escherichia coli" Bisensors Bioelectronics. 10. 601-605 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Utimoto: "A Preparation of β-Oxoester Enolate Equivalents from SMI_2 and α-Bromoalkanoates." Chem.Lett.197-198 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] K. Takai: "A Dramatic Effect of a Catalytic Amount of Lead on the Simmons-SmithReaction and Formation of Alkylzinc Compounds from Iodbalkanes. Reactivity of Zinc Metal:Activation and Deactivation," J.Org.Chem.59. 2671-2673 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K. Takai,: "Alkoxy-Directed Insertion of Carbon-Carbon Double Bonds into Tantalum-Alkyne Complexes. Chemo-and Stereoselective Addition of Alkenyl Groups to Olefins," J.Org.Chem.59. 5852-5853 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M. Aizawa: "Molecular Interfacing for Protein Molecular Devices and Neurodevices,I" Eng.Medicine and Biology,. 94-102 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K. Fujisawa: "Formation of a μ-η2:η2-Disulfide Dinuclear Copper(II) Complex by Thermal Decomposition of a Thiolate Complex via C-S Bond Cleavage," J.Chem.Soc.,Chem.Commun.623-623 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Murakami: "Photolysis of Hydrophbobic Vitamin B_<12> Derivatives Covalently Bound to lipid in Aqueous Meda," Chem.Lett.1657-1660 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 内本喜一朗: "有機金属化合物を用いる高選択的有機反応" 有機合成化学協会誌. 51. 1064-1073 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 内本喜一郎: "A Dramatic Effect of a Catalytic Amount of Lead on the Simmons-Smith Reaction and Formation of Alkylzinc Compounds from Iodo Alkanes.Reactivity of Zinc Metal" J.Org.Chem.(印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 碇山義人: "Electrochemiluminescent Sensing for the Characterization of DNA-interacting Antitumor and Antiviral Agents" Sensors & Actuators. 13-14. 725-727 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 北島信正: "Synthesis,Molecular Structure and Reactivity of (Alkylperoxo)copper(II) Complex" J.Am.Chem.Soc.115. 7872-7873 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 徳田昌生: "New Total Synthesis of (+)-N-Methylanisomycin by Aniodic Cyclization of δ-Alkenylamine" Tetrahedron. 49. 2413-2426 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 久枝良雄: "Enantioselective Alkylation of Hydrophobic Vitamin B_<12> Bearing a Binaphthyl Moiety" Chem.Lett.909-912 (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2018-02-02  

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