1996 Fiscal Year Final Research Report Summary
New Development of Electron Transfer in Co-ordination Compounds
| Project/Area Number |
05235106
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Research Institution | Kyoto University |
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Principal Investigator |
UTIMOTO Kiitiro Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (90025958)
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| 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)
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| Project Period (FY) |
1993 – 1995
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| Keywords | ELECTRON TRANSFER / STEREOSELECTIVE / DIMETALLIC REAGENT / ORGANOZINC COMPOUND / LEAD CATALYST / VITAMIN B_<12> / COORDINATION COMPOUND / BIOSENSING |
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| 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
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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
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