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オキサニッケラサイクルへのトランスメタル化を利用したヘテロ環の合成

Research Project

Project/Area Number 13029004
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionHokkaido University

Principal Investigator

森 美和子  北海道大学, 大学院・薬学研究科, 教授 (80001981)

Co-Investigator(Kenkyū-buntansha) 佐藤 美洋  北海道大学, 大学院・薬学研究科, 助教授 (90226019)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥17,000,000 (Direct Cost: ¥17,000,000)
Fiscal Year 2003: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥5,800,000 (Direct Cost: ¥5,800,000)
Fiscal Year 2001: ¥5,200,000 (Direct Cost: ¥5,200,000)
Keywords炭酸ガス / 炭酸ガス固定 / ニッケル錯体 / 亜鉛試薬 / トランスメタル化 / 4置換アルケン / シリルアセチレン / Ni(COD)_2 / ニッケル / carboxylation / Erythrina Alkaloid / Erythrocaline / メタセシス / メタラサイクル / 不斉環化 / ジルコナサイクル / エナンチオ場選択 / ローダサイクル / 7員環 / Rh錯体
Research Abstract

我々はこれまで3置換基オレフィンの合成について検討を加えてきた。更にその反応を利用してerythrocarineの合成にも成功した。それと並行して4置換オレフィンの合成にも検討を加えてきた。4置換オレフィンを合成するにあたっては位置選択性が非常に大きな問題となる。我々は末端にMe_3Si基をもつアルキンに対して本反応を検討することにした。末端にTMS基を持つアルキンを量論量のNi(cod)_2および2当量のDBUとともに常圧のCO_2雰囲気下撹拌し、その後亜鉛試薬を加えることによって4置換アルケンを合成することが出来る。その結果TMS基の影響でオキサニッケラサイクルの形成にかなり位置選択性が出ることが分かった。この反応の研究途上、本反応を触媒化することに成功した。我々は量論量のニッケル錯体を用いてきたが機構的にはニッケルは零化に戻るので触媒反応は成立すると思われてきた。しかし触媒量のニッケル錯体を用いて本反応を行うとほとんど反応は進行しない。種々考察した結果ニッケル錯体の配位子としてDBUを用いてきたが、DBUは亜鉛試薬にも配位するためではないかと思われた。そこで大過剰のDBU存在下10mol%のNi(cod)_2を用いたところ比較的良い収率で目的とする4置換オレフィンを合成することが出来た。更に興味深いことに用いた生成物を精査した結果、量論反応と触媒反応では異なる機構によって反応が進行しているように見えることである。この機構を解明すべく癌剤研究を行っている。本反応の適用範囲について検討を加え、早急にまとめて論文にしたい。

Report

(3 results)
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] Yoshihiro Sato, Yoshihiro Oonishi, Miwako Mori: "Novel Rhodium(I)-Catalyzed Cycloisomerization of 1,3-Diene with Alkene in a Tether : Competitive Reaction with a [4+2] Cycloaddition"Organometallics. 30-32 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yuji Kozawa, Miwako Mori: "Synthesis of 3-Alkoxycarbonyl-1β-Methylcarbapenem Using Palladium-Catalyzed C-N Bond-Forming Reaction Between Vinyl Halide and β-Lactam Nitrogen"J.Org.Chem.. 68. 3064-3067 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori, Tomoko Takaki, Muneyoshi Makabe, Yoshihiro Sato: "Zirconium-Catalyzed Enantiotopic Group-Selective Synthesis of Hydrindanes"Tetrahedron Letters. 44. 3797-3800 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori, Nozomi Saito, Daisuke Tanaka, Masanori Takimoto, Yoshihiro Sato: "Novel Alkenylative Cyclization Using a Ruthenium Catalyst"J.Am.Chem.Soc.. 125. 5606-5607 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masanori Takimoto, Mitsunobu Kawamura, Miwako Mori: "Nickel(0)-Mediated Sequential Addition of Carbon Dioxide and Aryl Aldehydes into Terminal Allenes"Nickel(0)-Mediated Sequential Addition of Carbon Dioxide and Aryl Aldehydes into Terminal Allenes"Organic Letters. 5. 2599-2601 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Kazuya Shimizu, Masanori Takimoto, Miwako Mori: "Novel Synthesis of Heterocycles Having Quaternary Carbon Center via Nickel-Mediated Carboxylation : Tatal Synthesis of Erythrocarine"Organic Letters. 5. 2323-2325 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori, Yuji Kozawa, Masanori Takimoto: "Novel Synthesis of Carbapenams Using Transition Metals"Synthetic Organic Chemistry Japan. 61. 25-32 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yuji Kozawa, Miwako Mori: "Synthesis of Carbapenam by Intramolecular Attack of Lactam Nitrogen toward η^1-Allenyl and η^3-Propargylpalladium Compex"J.Org.Chem.. 68. 8068 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato, Yoshihiro Oonishi, Miwako Mori: "Synthesis of Conjugated Dienes Attached to a Quaternary Carbon Center via Pd(0)-Catalyzed Deconjugative Allylation of Alkenylidenemalonates."J.Org.Chem.. (in press). (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori: "Ruthenium-Catalyzed ROM, RCM and CM of Enyne"Journal Molecular Catalysis. A, Chemical.. (in press). (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masanori Takimoto, Mitsunobu Kawamura, Miwako Mori: "Nickel-Mediated Regio- and Stereoselective Carboxylation of Tnimethylsilylallene under an Atmosphere of Carbon Dioxide"Synthesis. (in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Kozawa et al.: "Synthesis of Different Ring-Size Heterocycles from Same Propargyl Alcohol Derivative by Ligand Effect"Tetrahedron Letters. 43. 1499-1502 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Sato et al.: "A New Method for the Synthesis of Cycloheptenones via a Rh(I)-Catalyzed Intramolecular Hydroacylation of 4,6-Dienals"Angew. Chem. Int. Ed.. 41・7. 1208-1221 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Mori et al.: "Syntheses of Anolignans A and B Using Ruthenium-Catalyzed Cross-Enyne Metathesis"J. Org. Chem.. 67. 224-226 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Nakanishi et al.: "Total Synthesis of (-)-Strychnine"Angew. Chem. Int. Ed.. 41・11. 1934-1936 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Takirnoto et al.: "Novel Catalytic CO_2 Incorporation Reaction : Nickel-Catalyzed Regio-and Stereoselective Ring-Closing Carboxylation of Bis-1,3-dines"J. Am. Chem. Soc.. 124・34. 10008-10009 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Mori et al.: "Ruthenium-Catalyzed ROM-RCM of Cycloalkene-yne"Org. Lett.. 4・22. 3855-3858 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Masanori Takimoto, et al.: "Cross-Coupling Reaction of Oxo-π-allylnickel Complex Generated from 1,3-Diene under an Atmosphere of Carbon Dioxide"J. Am. Chem. Soc.. 123. 2895-2896 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Shinji Kuroda, et al.: "Formation of Silazirconacyclopentenes from Zirconium-Silene Complex and Alkynes and Their Reactivities"J. Am. Chem. Soc.. 123. 4139-4146 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tsuyoshi Kitamura, et al.: "Ruthenium-Catalyzed Ring-Opening and Ring Closing Enyne Metathesis"Organic Letters. 3. 1161-1163 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yuji Kozawa, et al.: "Construction of a Carbapenam Skeleton Using Palladium-Catalyzed Cyclization"Tetrahedron Letters. 42. 4869-4873 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tsuyoshi Kitamura, et al.: "Unexpected results of enyne metathesis using a ruthenium complex containing an N-heterocyclic carbene ligand"Chem. Commun.. 1258-1259 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masanori Takimoto, et al.: "Nickel-Promoted Alkylative Carboxylation of Alkynes"Organic Letters. 3. 3345-3347 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2018-03-28  

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