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金属錯体を経由する合成反応の理論計算に基づいた設計

Research Project

Project/Area Number 12042256
Research Category

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

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionNara University of Education

Principal Investigator

山邊 信一 (山辺 信一)  奈良教育大学, 教育学部, 教授 (00109117)

Co-Investigator(Kenkyū-buntansha) 山崎 祥子  奈良教育大学, 教育学部, 教授 (50182481)
Project Period (FY) 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2001: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2000: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywordsエンイン / ルイス酸 / 閉環反応 / 5員環化化合物 / シクロプロパン化 / セレノシリルエテン / ケテン / オキセタン
Research Abstract

ルイス酸によって促進される反応は有機合成に広く利用されている。最近、遷移金属を触媒とするエンイン環化反応が効率のよい合成反応として活発に行なわれているが、ルイス酸によるエンインの環化の報告例は少ない。我々は、ルイス酸による環化を引き起こすために、エンイン基質としてルイス酸配位可能なカルボニル基を3こ又は2こもつ反応性が高いエンインをデザインした。トリエステルまたは、ジエステル基質のルイス酸(塩化鉄、臭化亜鉛、ヨウ化亜鉛など)存在下での環化反応により、ハロゲン化水素付加環化合物を立体選択的に得た。本反応により、γ-ラクトン、シクロペンタン、γ-ラクタムを合成した。閉環反応の機構について、γ-ラクトン生成を例にとり、考察した。特に、環化段階におけるアルキンのルイス酸への配位と効率的環化に関する役割について、理論計算を用いて調べた。構造最適化はSCRF溶媒効果を含んだB3LYP法で行ない、基底関数として6-31G^*を用いた。モデル化合物としてエンインと臭化亜鉛の反応の計算を行なった。閉環前駆体ZnBr_2錯体において求核性アルキンの炭素がZnBr_2が配位した求電子性オレフィンの炭素を攻撃し、閉環の遷移状態を経て、双性イオンを与える。続いて、双性イオンのBr^-の分子間における立体的に有利なtrans付加が起こり、閉環中間体となる。プロトンが付加し、ブロモ-γ-ラクトンとなることがわかった。閉環前駆体において、結合が形成するC---Cの距離は2.860Åで既に短く、環化が容易に起こる構造である。閉環のエネルギー障壁は5.3kcal/molで環化が容易な過程であることがわかった。アルキンの直交する2つのp_π軌道のいずれかが空間的に自由にアルケンの求電子性中心の方向に向くことができると考えられる。双性イオンのビニルカチオン炭素とBr_2Zn-(CO_2Me)_2C-CH_3^-fのBrを3.5Åの距離に置き初期構造とし、構造最適化したところ、臭素は容易に炭素に結合した。従って、双性イオン分子間のBr^-のリレーにより、閉環中間体が生成すると考えられる。

Report

(2 results)
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Yamazaki, S.: "Olefin-olefin Reactions Mediated by Lewis Acids may Afford Cyclopropanes rather than Cyclobutanes : Mechanistic Study of Cyclopropane Formation using a 1-Seleno-2-silylethene"J. Chem. Soc., Perkin Trans. 2. 164-173 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hiraoka, K.: "A Gas-phase Polymerization Reaction in the Cluster Ion NO^+(propylene)_n"Chem. Phy. Lett.. 349. 313-320 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yamabe, S.: "Norcaradiene Intermediates in Mass Spectral Fragmentations of Tropone and Tropothione."J. Chem. Soc., Perkin Trans. 2. 2202-2210 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Okumoto, S.: "Water-trimer Clusters as Nucleophilic Reagents in Hydrolyses of Substrates for Metal-alkoxides -A Computational Study"J. Non-Cryst. Solids. 291. 167-175 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yamabe, S.: "A Jahn-Teller Geometric Distortion Effect on the Woodward-Hoffmann Rule in Thermal Decompositions of Diazetines"J. Phys. Chem. A. 105. 7281-7286 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hiraoka, K.: "Characteristic Charges of Bond Energies for Gas-Phase Cluster Ions of Halide Ions with Methane and Chloromethanes"J. Phys. Chem. A. 105. 4887-4893

    • Related Report
      2001 Annual Research Report
  • [Publications] Okumoto, S: "A Computational Study of Base-catalyzed Reaction between Isocyanates and Epoxides Affording 2-Oxazolidones and Isocyanurates"J. Comput. Chem.. 22. 316-326 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hiraoka, K.: "Hydrogen Bonds in Gas-Phase Clusters Between Halide Ions and Olefins"J. Am. Soc. Mass Spectrum. 12. 144-149 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yamabe, S.: "Norcaradiene Intermediates in Mass Spectral Fragmentations of Tropone and Tropothione"J. Chem. Soc., Perkin Trans. 2. 2202-2210 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Okumoto, S.: "Water-trimer Clusters as Nucleophilic Reagents in Hydrolyses of Substrates for Metal-alkoxides -A Computational Study"J. Non-Cryst. Solids. 291. 167-175 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yamazaki, S.: "First Example of A Lewis-Acid Promoted [2+1] Cycloaddition of A 1-Thio-2-silylethene"J. Org. Chem.. 66. 5915-5918 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yamazaki, S.: "Synthesis of Novel All-cis-functionalized Cyclopropane Template-assembled Collagen-Models"J. Chem. Soc., Perkin Trans. 1. 1870-1875 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yamazaki, S.: "A Novel Lewis Acid-promoted Enyne Cycloisomerization of Triester-substituted Alkenes"J. Chem. Soc., Chem, Commun.. 69-70 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Okumoto,S.: "A Computational Study of Base-catalyzed Reaction between Isocyanates and Epoxides Affording 2-oxazolidones and Isocyanurates."J.Computational Chem.. (in press.).

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamabe,S.: "A Mechanism of the Ion Separation of the NaCl Microcrystal via the Association of Water Clusters."J.Phys.Chem.B. 104. 10242-10252 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Hiraoka,K.: "On the Structure and Stability of Gas-Phase Cluster Ions SiF_3^+(CO)_n, SiF_3OH_2^+(SiF_4)_n, SiF_4H^+(SiF_4)_n, and F^-(SiF_4)_n."J.Phys.Chem.A. 104. 8353-8359 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Hiraoka,K.: "Dimer Formation of NO Ligands in the Gas-Phase Halide Ion Clusters X(NO)_n Enhanced by a Frontier Orbital Interaction."Chem.Phy.Lett.. 323. 155-159 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Nakata,S.: "Mechanism of Nonlinear Responses of a Semiconductor Gas Sensor."Instrumentation Science & Technology. 28. 241-251 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamabe,S.: "A Three-Center Orbital Interaction in the Diels-Alder Reactions Catalyzed by Lewis Acids."J.Org.Chem.. 65・6. 1830-1841 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Okumoto,S.: "A Theoretical Study of Curing Reactions of Maleimide Resins through Michael Additions of Amines."J.Org.Chem.. 65・5. 1544-1548 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamazaki,S.: "Olefin-olefin Reactions Mediated by Lewis Acids may Afford Cyclopropanes rather than Cyclobutanes : Mechanistic Study of Cyclopropane Formation using a 1-Seleno-2-silylethene."J.Chem.Soc.,Perkin Trans.2. 164-173 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamazaki,S.: "A Novel Lewis Acid-promoted Enyne Cycloisomerization of Triester-substituted Alkenes."J.Chem.Soc.,Chem.Commun.. 69-70 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamazaki,S.: "The Mechanism of [2+1] and [2+2] Cycloaddition Reactions of 1-(Phenylseleno)-2-(trimethylsilyl) ethene : An Isotopic Labelling Study."J.Chem.Soc.,Perkin Trans.1. 1991-1996 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamazaki,S.: "Cyclization Reactions using Vinyl Sulfides and Vinyl Selenides : Recent Developments towards Organic Synthesis."J.Synth.Org.Chem.Jpn.. 58・1. 50-61 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2018-03-28  

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