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Dynamic Control of Stereochemistry in Carbon-Carbon and Carbon-Silicon Bonds Formations through Electron Transfer Reaction

Research Project

Project/Area Number 10208205
Research Category

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

Allocation TypeSingle-year Grants
Research InstitutionNagaoka University of Technology

Principal Investigator

NISHIGUCHI Ikuzo  Nagaoka University of Technology, Faculty of Engineering ; Professor, 工学部, 教授 (20026347)

Co-Investigator(Kenkyū-buntansha) OHMORI Hidenobu  Osaka University, Graduate School of Pharmacology ; Professor, 大学院・薬学研究科, 教授 (90028845)
NONAKA Tsutomu  Turuoka National College of Technology ; Principle, 校長 (00016528)
MAEKAWA Hirofumi  Nagaoka University of Technology, Faculty of Engineering ; Assistant Professor, 工学部, 助手 (70283041)
Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥48,700,000 (Direct Cost: ¥48,700,000)
Fiscal Year 2000: ¥16,100,000 (Direct Cost: ¥16,100,000)
Fiscal Year 1999: ¥16,100,000 (Direct Cost: ¥16,100,000)
Fiscal Year 1998: ¥16,500,000 (Direct Cost: ¥16,500,000)
KeywordsElectron transfer reaction / Stereoselective reaction / Magnesiun metal / Carbon-acylation / Carbon-silylation / Electroreduction / (Z)-α-Chloroglycidyl esters / Irradiation of ultrasounds / 環開裂反応 / ヘテロ環飽和化合物 / 還元的脱離反応 / オレフィンアルコール / 立体特異性 / 超音波照射 / 立体化学効果 / 高立体選択的 / 高位置選択的 / クマリン誘導体 / ジハイドロピリジン類 / 高立体選択性 / 分子内環化反応 / 炭素-炭素結合形成反応 / シス-ジアルキルピロリジノール / (Z)-クロログリシジルエステル / 反応性金属陽極 / 還元的クロスカップリング
Research Abstract

In this study, highly regio- and stereoselective carbon-carbon and carbon-silicon bonds formations, which cannot be observed in a homogeneous solution, have been developed through dynamic control of stereochemistry of reactive intermediates generated on a heterogeneous interface between solid and liquid by electron transfer reactions from metals or electrodes to organic compounds. For example, treatment of 3-alkylcoumarins as typical aromatic α,β-unsaturated esters with acid anhydrides in the presence of easily available Mg turning without any pre-treatment brought about highly regio- and stereoselective C-acylation to give the thermodynamically unfavorable cis-3-alky-4-acyldihydrocoumarins with stereo-selectivity of 92-98%. Under the similar reaction conditions, high regio- and stereoselectivities were also observed in the Mg-promoted silylation of 3-alkylcoumarins and dimethyl 1,2-dihydro-2,3-pyridinedicarboxylates.
On the other hand, (Z)- and (E)-3-buten-1-ols were exclusively obtained in the stereospecific manner from electroreductive ring-cleavage of cis- and trans- 2-substituted-3-chlorotetrahydrofurans, respectively. Furthermore, electroreduction of methyl trichloroacetate in the presence of aliphatic aldehydes using a reactive Zn anode resulted in stereoselective corss-coupling giving (Z)-α-chloroglycidyl esters. Also, remarkable stereoselectivity control by irradiation of ultrasounds onto the electorode surface was successfully established in the electroreductive dimerization of acetophenone and debromination of dl-1,2-dibromoethanes.

Report

(4 results)
  • 2001 Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (44 results)

All Other

All Publications (44 results)

  • [Publications] 西口郁三: "Highly Selective and Facile Synthesis of Dihydro- and Tetrahydropyridine Dicarboxylic Acid Derivatives Using Electroreduction as a Key Step"Tetrahedron. (in press). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 西口郁三: "Facile Iodonation of Terminal Acetylenes by Anodic Oxidation in the Presence of NaI"Synlett. 89-91 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 西口郁三: "Facile O-Silylation of Tertiary Alcoholsin the Presence of Mg-Metal"Synlett. 1025-1027 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 西口郁三: "Facile Synthesis of Silyl Enol Ethers by Mg-Promoted Coupling of Aliphatic Carbonyl Compounds with Trimethylsilyl Chloride"Tetrahedron Lett. 40. 1349-1352 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 野中 勉: "Ultrasonic Effects on Electroorganic Processes. Part 14. Indirect Electroreduction of Benzyl Chlorides with an Anthracene Redox-mediatory System"Ultrasonics Sonochemistry. 7. 97-102 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 大森秀信: "Reactions of Grignard Reagents with Bis- or Mono-Phosphonium Ions InSitu Generated from Bu3P and Dicarboxylic Acid Dichlorides or ω-Ethoxycarbonyl Alkanoyl Chlorides as a Novel Method to Obtain Diketones and Ketoesters"Chem.Pharm.Bull.. 48. 1196-1199 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 西口郁三(分担執筆): "電気化学便覧第5版(電気化学協会編)「電極化学材料-電解液、電解槽、隔膜」"丸善. 756 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 野中 勉: "New Concepts and Methodologies for Electrode Interface Modefication, New Callenges in Organic Electrochemisty"Gordon and Breach Sci. 330 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. Kita, H. Maekawa, Y. Yamasaki, I. Nishiguchi: "Highly Selective and Facile Synthesis of Dihydro- and Tetrahydropyridine Dicarboxylic Acid Derivatives Using Electroreduction as a Key Step"Tetrahedron. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K. Itoh, S. Shino, H. Maekawa, I. Nishiguchi: "Novel Synthesis of 2-Arylcyclohexanones using Anodic Oxidation of Enol Acetates as the Key Step"J. Electroanal. Chem.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I. Nishiguchi, S. Goda, T. Kikkawa, Y. Ishino, H. Maekawa: "Selective Synthesis of α-Chloroepoxides by Electroreductive Cross-Coupling of Methyl Trichloroacetate with Aliphatic Aldehydes Using Reactive Metal Electrode"J. Electroanal. Chem.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I. Nishiguchi, O. Kambe, K. Itoh, H. Maekawa: "Facile Iodonation of Terminal Acetylenes by Anodic Oxidation in the Presence of NaI"Synlett.. 89-91 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I. Nishiguchi, Y. Kita, M. Watanabe, Y, Ishino, T, Ohno, H. Maekawa: "Facile O-Silylation of Tertiary Alcohols in the Presence of Mg-Metal"Synlett.. 1025-1027 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I. Nishiguchi, K. Itoh, H. Maekawa: "Electrochemical Hydrocoupling of Acetylene Derivatives by Anodic Oxidation of NaBH_4"Electrochemica Acta. 45. 2991-2993 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. Kita, H. Maekawa, Y. Yamasaki, I. Nishiguchi: "Selective and Facile Electroreductive Synthesis of Dihydro- and Tetrahydro- pyridine Dicarboxylic Acid Derivatives,"Tetrahedron Lett.. 40. 8587-8590 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. Ishino, Y. Kita, H. Maekawa, T. Ohno, Y. Yamasaki, T. Miyata, I. Nishiguchi: "Facile Synthesis of Silyl Enol Ethers by Mg-Promoted Coupling of Aliphatic. Carbonyl Compounds with Trimethylsilyl Chloride"Tetrahedron Lett.. 40. 1349-1352 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. ATOBE, T. NONAKA: "Preparation and Application of Electroconductive Films Electrooxidatively Polymerized in Ultrasonic and Centrifugal Acceleration Fields,"Trans. Mat. Res. Soc. Jpn.. 25(1). 81-85 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. KADO, M. ATOBE, T. NONAKA: "Ultrasonic Effects on Electroorganic Processes. Part 18. A Limiting Current Study on Indirect Electrooxidation of n-Butylamine with a Triarylamine Redox Mediator,"Electrochemistry. 68(4). 262-266 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Atobe, Y. Kado, T. Nonaka: "Ultrasonic Effects on Electroorganic Processes. Part 14. Indirect Electroreduction of Benzyl Chlorides with an Anthracene Redox-mediatory System,"Ultrasonics Sonochemistry. 7. 97-102 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Atobe, M. Sssahira, T. Nonaka: "Ultrasonic Effects on Electroorganic Processes. Part 17. Product Selectivity Control in Cathodic Reduction of Acrylonitrile,"Ultrasonics Sonochemistry. 7. 103-107 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Atobe, K. Sato, T. Nonaka: "Ultrasonic Effects on Electroorganic Processes. Part 19. Cathodic Reduction and Adsorption of p-Methylbenzaldehyde on a Liquid Mercury Electrode,"Electrochemistry. 69. 10-15 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H. Maeda, N. Hino, Y. Yamauchi, H. Ohmori: "Reactions of Grignard Reagents with Bis- or Mono-Phosphonium Ions In Situ Generated from Bu_3P and Dicarboxylic Acid Dichlorides or β-Ethoxycarbonyl Alkanoyl Chlorides as a Novel Method to Obtain Diketones and Ketoesters"Chem. Pharm. Bull.. 48. 1196-1199 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H. Maeda, Y. Huang, Y. Yamauchi, H. Ohmori: "Reduction of Benzoyl Tributylphosphonium Chlorides by Samarium Diiodide as a Novel Access to 4-Benzoyl Benzaldehydes"Chem. Commun.. 2307-2308 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. Ishino, M. Mihara, S. Nishihama, I. Nishiguchi: "Zinc Metal-Promoted Stereoselective Olefination of Aldehydes and Ketones with gem-DichloroCompounds in the Presence of Chlorotrimethylsilane."Bull. Chem. Soc. Jpn. 71. 2669-267 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 西口郁三: "Facile Iodonation of Terminal Acetylenes by Anodic Oxidation In the Presence of NaI"Synlett.. 89-91 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 西口郁三: "Facile O-Silylation of Tertiary Alcohols in the Presence of Mg-Metal"Synlett. 1025-1027 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 西口郁三: "Electrochemical Hydrocoupling of Acetylene Derivatives by Anodic Oxidatio of NaBH_4"Electrochem.Acta. 45. 2993-2995 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 西口郁三: "Highly Selective and Facile Synthesis of Dihydro- and Tetrahydropyridine Dicarboxylic Acid Derivatives Using Electroreduction as a Key Step"Tetrahedron. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 野中勉: "Ultrasonic Effects on Electroorganic Processes Part14.Indirect Electroredu of Benzyl Chlorides with an Anthracene Redox-mediatory System"Ultrasonics Sonochemistry. 7. 97-102 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 大森秀信: "Reduction of Benzoyl Tributylphosphonium Chlorides by Samarium Diiodide as a Novel Access to 4-Benzoyl Benzaldehydes"Chem.Communi,.. 2307-2308 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 野中勉(分担執筆): "Stereochemistry of Organic Electrode Processes,"Organic Electrochemistry 4th.Ed",(ed.by H.Lund and O.Hammerich)"Marcal Dekker. 1399 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 西口郁三(分担執筆): "電気化学便覧第5版(電気化学協会 編)「電極化学材料-電解液、電解槽、隔膜」"丸善(株). 756 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] 喜多圭郎: "Selective and Facile Electroreductive Synthesis of Dihydro- and Tetrahydropyridine Dicarboxylic Acid Derivatives"Tetrahedron Lett. 40(49). 8587-8590 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 西口郁三: "Facile Iodination of Terminal Acetylenes by Anodic Oxidation in the Presence of NaI"Synlett. in press. (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] 石野義夫: "Facile Synthesis of Silyl Enol Ethers by Mg-Promoted Coupling of Aliphatic Carbonyl Compounds with Trimethylchlorosilane"Tetrahedron Lett. 40(7). 1349-1352 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 前川博史: "反応性金属陽極を用いた新規炭素-炭素結合形成を目指す有機電解反応"電気化学および工業物理化学. 67(8). 875-877 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 前田初男: "Electrochemistry of Phosphorusand Sulfur Compounds : A Unique Tool for Organic Synthesis"Accounts of Chemical Research. 32(1). 72-80 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 跡部真人: "Ultrasonic Effects on Electroorganic Processes. Part 16. Stereoselectivity Control of Hydrodimers Formed in Cathodic Reduction of Acetophenones"Electrochem. Commun. 1(7). 593-596 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 石野義夫: "Facile Synthesis of Silyl Enol Ethers by Mg-Promoted Coupling of Aliphatic Carbonyl Compounds with Trimethylsilyl Chloride" Tetrahedron Letters. 40巻7号. 1349-1352 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 石野義夫: "Zinc Metal-Promoted Stereoselective Olefination of Aldehydes and Ketones with gem-Dichloro Compounds in the Presence of Chlorotrimethylsilane." Bull.Chem.Soc.Jpn. 71巻. 2669-2672 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 津田良弘: "Dioxygen-Activated Reductive Epoxydation of Cyclohexene using Mn(III) porphyrin as Catalyst and Hexylviologen as electron Mediator" J.Mol.Catal.A:Chem. 115巻. 1932-1940 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 津田良弘: "ビオロゲンを電子メデイエーターとして含むポルフィリン系を一酸化原子添加触媒として用いたシクロヘキセンのエポキシ化" 日本化学雑誌. 9号. 581-590 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 前田初男: "Electrochemistry of Phosphrus and Sulfur Compounds:A Unique Tool for Organic Synthesis." Accounts of Chemical Reseach. 32. 72-80 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 跡部真人: "Frequency Effect of Ultrasound on Debromination of Stilbenedibromides with Zinc Powder." Chem.Lett. 7号. 699-700 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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