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Clarification of the Reduction Behaver of Photoexcited Samarium Species and its Application to the Development of New Synthetic Process

Research Project

Project/Area Number 10555315
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 有機工業化学
Research InstitutionOsaka University

Principal Investigator

OGAWA Akiya  Graduate School of Engineering, Osaka University, Associate Professor, 大学院・工学研究科, 助教授 (30183031)

Co-Investigator(Kenkyū-buntansha) HIRAO Toshikazu  Graduate School of Engineering, Osaka University, Professor, 大学院・工学研究科, 教授 (90116088)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
KeywordsSamarium Diiodide / Photoexcitation / Carbonylation / Chemoselective Reduction / Rare Earth Catalytic System / Carbon-Carbon Bond Formation / Electron-Transfer / Carbon Monoxide / ヨウ化イッテルビウム / 一電子還元 / ラジカル還化 / 還元 / 還元的脱ハロゲン化 / 還元的脱セレノ化
Research Abstract

It has been revealed that the irradiation with visible light enhances the reducing ability of samarium diiodide. While the reduction of organic chlorides with SmIィイD22ィエD2 alone is difficult, irradiation with visible light causes the efficient reduction of organic chlorides to the corresponding hydrocarbons. Upon irradiation with visible light, gem-dichlorocyclopropanes undergo reductive dechlorination with samarium diiodide and benzenethiol to provide the corresponding cyclopropanes in good yields. The reaction may proceed via the hydrogen abstraction from PhSH by cycolopropyl radicals formed in situ by the reduction with SmIィイD22ィエD2. A novel photoinduced reduction of group 16 heteroatom compounds such as organic selenides, tosylates, and tellurides has also been developed. In particular, organic selenides, which can not be reduced with SmIィイD22ィエD2 in the dark (or even in the presence of HMPA), undergo reductive cleavage efficiently by using the SmIィイD22ィエD2-hv system. Moreover, the photoinitiated reaction of alkyl chlorides (R-Cl) with SmIィイD22ィエD2 in the presence of carbon monoxide (50 atm) is examined. The reaction provides the corresponding asymmetrical ketones (RC(=O)CHィイD22ィエD2R) as a carbonylated product. A mechanistic proposal includes the dimerization of acylsamarium species formed in situ by the reductive carbonylation of alkyl chlorides with CO and SmIィイD22ィエD2. Irradiation with near-UV light dramatically also enhances the reducing ability of ytterbium diiodide (YbIィイD22ィエD2). Organic bromides, iodies, tosylates, and tellurides are reduced efficiently by a YbIィイD22ィエD2-hv system, while these can not be reduced with YbIィイD22ィエD2 in the dark.

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] Akiya Ogawa: "Diastereoselective Pinacol Coupling of Alleyl Arul Ketones with Rare Earth Metals in the Presence of Chlorosilanes"Tetrahedron Lett.. 40・39. 7113-7114 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Akiya Ogawa: "Photoinduced Reduction of Group 16 Heteroatom Compounds with the Aid of Samarium Diiodide"Tetrahedron Lett.. 39・35. 6341-6342 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 小川昭弥: "希土類光還元系の開発"生産技術誌. 50・2. 53-55 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ogawa, H. Takeuchi, T. Hirao: "Diastereoselective Pinacol Coupling of Alkyl Aryl Ketones with Rare Earth Metals in the Presence of Chlorosilanes"Tetrahedron Lett.. 40 (39). 7113-7114 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ogawa, S. Ohya, M. Doi, Y. Sumino, N. Sonoda, T. Hirao: "Photoinduced Reduction of Group 16 Heteroatom Compounds with the Aid of Samarium Diiodide"Tetrahedron Lett.. 39 (35). 6341-6342 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ogawa: "Development of New Photoinduced Reduction System by Use of Rare Earth Compounds"The Production & Thchnique. 50 (2). 53-55 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Akiya Ogawa: "Diastereoselective Pinacol Coupling of Alkyl Aryl Ketones with Rare Earth Metals in the Presence of Chlorosilanes"Tetrahedron Lett.. 40・39. 7113-7114 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akiya Ogawa: "Photoinduced Reduction of Group 16 Heteroatom Compounds with the Aid of Samarium Diiodide" Tetrahedron Letters. 39巻35号. 6341-6342 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 小川昭弥: "希土類光還元系の開発" 生産技術誌. 50巻・2号. 53-55 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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