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Studies on catalysts for selective functionalization of Group 14 compounds

Research Project

Project/Area Number09650953
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionHOKKAIDO UNIVERSITY(1998)
Gifu University(1997)

Principal Investigator

TSUJI Yasushi  Catalysis Research Center, Hokkaido Univ., Pro., 触媒化学研究センター, 教授 (30144330)

Co-Investigator(Kenkyū-buntansha) 川村 尚  岐阜大学, 工学部, 教授 (40026125)
Project Period (FY) 1997 – 1998
Project Status Completed(Fiscal Year 1998)
Budget Amount *help
¥3,000,000 (Direct Cost : ¥3,000,000)
Fiscal Year 1998 : ¥1,300,000 (Direct Cost : ¥1,300,000)
Fiscal Year 1997 : ¥1,700,000 (Direct Cost : ¥1,700,000)
Keywordsfunctionalization / cyanation / palladium catalyst / catalyst species / oxidative addition / fluxional / 触媒素反応 / 酸化的付加反応 / ビス(シリル)錯体 / ビス(スタニル)錯体 / 単分子分子内回転 / X線構造 / 錯体触媒 / 反応機構 / 白金錯体 / パラジウム錯体
Research Abstract

Allylic carbonates are cyanated in high yields to beta, gamma-unsaturated carbonitriles using trimethylsilyl cyanide in the presence of catalytic amount (5 mol%) of Pd(PPh_3)_4 in THF under reflux. The cyanations of several cis- and trans-alicyclic substrates proceed cleanly (stereoselectivity> 99%) with overall retention. Characterization and reaction of palladium complexes relevant to the present catalysis indicate that transmetallation of eta^3-allyl palladium complex with trimethylsilyl cyanide is facile, while the resulting cyano(eta^3-allyl)palladium complexes afford the corresponding allylic cyanides only when excess trimethylsilyl cyanide is present. Stereochemistry of the product indicates that the CN attacks the eta^3-allyl moieties from the palladium side.
The structures and fluxional behavior of two cis-bis(silyl)bis(phosphine)platinum complex, cis- [Pt(SiPh_2Me)_2(PMe_2Ph)_2] and cis-[Pt(SiFMe_2)_2(PEt_3)_2], and two cis-bis(stannyl)bis(phosphine)palladium complex, cis-[Pd(SnMe_3)_2(PMe_3)_2] and cis-[Pd(SnMe_3)_2(PMePh_2)_2], were examined, The complexes have twisted square-planar structures with cis-orientation of the ligands. The bis(silyl)platinum complexes show fluxional behavior on the NMR time-scale. In the fluxional process, the spin-spin coupling between P, Si, and Pt are retained ; namely these nuclear spin states are intramolecularly conserved. The fluxionality of the complexes is attributed to the unimolecular twist-rotation via pseudo tetrahedral transition state. Similar fluxionality of the bis(stannyl)palladium complex is evident by utilizing both solution and solid state ^<31>P NMR.

Report

(3results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report

Research Products

(7results)

All Other

All Publications

  • [Publications] Y.Tsuji: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis(silyl)-bis(phosphine)platinum and cis-Bis(stannyl)bis(phosphine)palladium Complexes" Organometallics. 17. 507-512 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Tsuji: "Palladium-Complex-Catalyzed Cyannation of Allylic Carbonates and Acetates Using Trimethylsilyl Cyanide" Organometallics. 17. 4835-4841 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Tsuji et al.: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis (silyl) bis (phosphine) platinum and cis-Bis (stannyl) bis (phosphine) palladium Complexes" Organometallics. 17. 507-512 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Tsuji et al.: "Palladium-Complex-Catalyzed cyanation of Allylic Carbonates and Acetates Using Trimethylsilyl Cyanide" Organometallics. 17. 4835-4841 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Tsuji: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis (silyl) bis (phosphine)-platinum and cis-Bis (stannyl) bis (phosphine) palladium Complexes" Organometallics. 17. 507-512 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Tsuji: "Palladium-Complex-Catalyzed Cyannation of Allylic Carbonates and Acetates Using Trimethylsilyl Cyanide" Organometallics. 17. 4835-4841 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Tsuji, K.Nishiyama, S-I.Hori, M.Ebihara, T.Kawamura: "Structure and Facile Urimolecular Twist-Rotation of cis-Bis(silyl)bis(phosphine)-platinum and cis-Bis(stannyl)bis(phosphine)palladium Conplexes" Organometallics. 17(印刷中). (1998)

    • Related Report
      1997 Annual Research Report

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Published : 1997-04-01   Modified : 2016-04-21  

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