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2002 Fiscal Year Final Research Report Summary

Control of Electron Transfer Reactions on the Basis of Dynamic Intramolecular Coordination

Research Project

Project/Area Number 13640532
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

SUGA Seiji  Graduate School of Engineering, Synthetic Chemistry and Biological Chemistry, Lecturer, 工学研究科, 講師 (50291430)

Project Period (FY) 2001 – 2002
Keywordselectron Transfer / organosilicon compound / cation rdical / electrolysis / pyridylethyl group / Dynamic Intramolecular Coordination
Research Abstract

The present work stems from our earlier observations that the introduction of carbonyl, alkoxy, and pyridyl groups decreases the oxidation potential of tetraalkylstannanes. There is no indication of the coordination in the neutral molecule by the spectroscopy. Therefore, the decrease of the oxidation potential seems to be attributed to the dynamic intramolecular coordination to tin in the cation radical intermediates. Such coordination stabilizes the cation radical which in turn favors the electron transfer and also controls the selectivity of the bond cleavage. Pyridyl group has been found to be especially effective among the examined.
Thus new class of electroauxiliary, [2-(2-pyridyl)etyl]dimethylsilyl group has been developed. Introduction of 2-(2-pyridyl)ethyl group on silicon atom of α-silylethers and sulfides gives rise to decrease of their oxidation potentials. Studies based on NMR spectra, ab initio molecular orbital calculations, and solvent effect of oxidation have suggested that the decrease of the oxidation potentials is attributed to the 'dynamic intramolecular coordination' of pyridyl group to silicon. The reactivity of this new electroauxiliary has been compared with those of trimethylsilyl group and tributylstannyl group by competition experiments. The present study indicates the feasibility of fine tuning of the reactivity of electroauxiliaries using dynamic intramolecular coordination.

  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] Suga, S., Suzuki, S., Yoshida, J.: "Reduction of a "Cation Pool". A New Approach to Radical Mediated C-C Bond Formation"Journal of the American Chemical Society. 124. 30-31 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshida, J., Suga, S: "Basic Concepts of"Cation Pool"and "Cation Flow"Methods and Their Applications in Conventional and Combinatorial Organic Synthesis"Chemistry-A European Journal. 8. 2650-2658 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Suga, S., Watanabe, M., Yoshida, J.: "Electroauxiliary-Assisted Sequential Introduction of Two Carbon Nucleophiles on the Same α-Carbon of Nitrogen : Application to the Synthesis of Spiro Compounds"Journal of the American Chemical Society. 124. 14824-14825 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Suga, S., Nagaki, A., Yoshida, J.: "Highly Selective Friedel-Crafts Monoalkylation Using Micromixing"Chemical Communications. 354-355 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 吉田潤一, 菅 誠治: "カチオンフロー法を用いたシリアルコンビナトリアル合成"有機合成化学協会誌. 60. 482-483 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Suga, S. ; Suzuki, S. ; Yoshida, J.: "Reduction of a Cation Pool A New Approach to Radical Mediated C-C Bond Formation"Journal of the American Chemical Society. 124. 30-31 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshida, J. ; Suga, S: "Basic Concepts of Cation Pool and Cation Flow Methods and Their Applications in Conventional and Combinatorial Organic Synthesis"Chemistry- A European Journal. 8. 2650-2658 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Suga, S. ; Watanabe, M. ; Yoshida, J.: "Electroauxiliary-Assisted Sequential Introduction of Two Carbon Nucleophiles on the Same α-Carbon of Nitrogen : Application to the Synthesis of Spiro Compounds"Journal of the American Chemical Society. 124. 14824-14825 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Suga, S. ; Nagaki, A. ; Yoshida, J.: "Highly Selective Friedel-Crafts Monoalkylation Using Micromixing"Chemical Communications. 354-355 (2002)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2004-04-14  

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