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Transition-Metal Catalyzed Novel and Useful C-C Bond Formation and Cleavage

Research Project

Project/Area Number 11450351
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNagasaki University

Principal Investigator

TAMARU Yoshinao  Nagasaki University, Professor, 工学部, 教授 (80026319)

Co-Investigator(Kenkyū-buntansha) TANAKA Shuji  Nagasaki University, Associate Professor, 工学部, 助教授 (80217033)
Project Period (FY) 1999 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥14,400,000 (Direct Cost: ¥14,400,000)
Fiscal Year 2002: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2001: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2000: ¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 1999: ¥4,700,000 (Direct Cost: ¥4,700,000)
Keywordspalladium / triethlylborane / diethylzinc / allyl alcohol / allylation / alkylation / H2O tolerance / amphiphillic activation / environment / aldehyde / 親電子的アリル化 / アリルアルコール / トリエチレンホウ素 / 極性転換 / アリル化 / 活性メチレン化合物 / アルキルアルデヒド / 極性転移 / アルデヒド
Research Abstract

Allyl alcohols are the most useful allyl carbon source, since they are stable, cheep, ubiquitous in nature. However, they have utilized scarcely as C3-unit owing to their low chemical reactivity. This research have disclosed the potential of allyl alcohols as the C-3 unit; they serve not only as allyl cations, but also as allyl anions in the catalytic reactions of palladium in the presence of Et3B or Et2Zn. That is, Pd-Et3B promotes 1) allylation of active methylene compounds, 2) amines, 3) α-position of aldehydes. On the other hand, Pd-Et3B or Pd-Et2Zn helps nucleophilic allylation of aldehydes and ketones by direct use of allyl alcohols themselves. All these reactions proceed at room temperature and even in the presence of water. All these features associated with the use of an allyl alcohol as a starting material combine to contribute to academic advancement, also to creating reactions that are environmentally friendly and economically advantageous.

Report

(5 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (46 results)

All Other

All Publications (46 results)

  • [Publications] 木村正成 他 3名: "Ni(0)-Catalyzed Three-Component Connection Reaction of Dimethylzinc, 1,3-Dienes, and Carbonyl Compounds"Angew. Chem. Int. Ed.. 38. 3386-3388 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 木村正成 他 5名: "Nickel-Catalyzed Homoallylation of Aldehydes and Ketones with 1,3-Dienes and Complementary Promotion by Diethylzinc and Triethylborane"Angew. Chem. Int. Ed.. 38. 397-400 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 柴田和文 他 3名: "Nickel-Catalyzed Intramolecular Homoallylation of ω-Dienyl Aldehyde"Org. Lett.. 3. 2181-2183 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 木村正成 他 3名: "Nickel-catalyzed homoallylation of Aldehyde in the Presence of Water and Alcohols"Angew. Chem. Int. Ed.. 40. 3600-3602 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 木村正成 他 4名: "Strikingly Simple Direct α-Allylation of Aldehydes with Allyl Alcohol : Remarkable Advance in the Tsuji-Trost Reaction"J. Am. Chem. Soc.. 123. 10401-10402 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 江副昭宏 他 4名: "Remarkably High 1,5-Asymmetric Induction in a Nickel-Catalyzed Through Space Conjugative Addition of Me2Zn and Carbonyls across 1,ω-dienynes"Anew. Chem. Int. Ed.. 41. 2784-2786 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 田丸良直: "Palladium-Catalyzed Reaction of Allyl and Related Derivatives with Organoelectrophiles in Handbook of Organopalladium Chemistry for Organic Synthesis, E. Negishi, Ed"Wiley. 123 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kimura I. Kiyama, T Tomizawa, Y. Horino, S. Tanaka, Y. Tamaru: "Palladium-Catalyzed Allylation of Aldehydes via Umpolung of π-Allylpalladium by Triethylborane"Tetrahedron Lett.. 40. 6795-6798 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y Horino, M. Kimura, M. Naito, S. Tanaka, Y. Tamaru: "Novel 1,3-Sulfonyl Shift and [4+2] Cycloaddition Reaction of N-Allenyl Sulfonamide Promoted by Allylsilane"Tetrahedron Lett.. 41. 3427-3431 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kimura, T. Tomizawa, Y. Horino, S. Tanaka, Y. Tamaru: "Et_3B- Pd-promoted Allylation of Benzaldehyde with Allylic Alcohols"Tetrahedron Lett.. 41. 3627-3629 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Tamaru. Y. Horino M. Araki, S. Tanaka, M. Kimura: "Et_3B- promoted, Pd^0-catalysed Allylation of Active Methylene Compounds with Allylic Alcohols"Tetrahedron Lett.. 41. 5705-5709 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kimura, K. Shibata, Y. Koudahashi, Y. Tamara: "Ni^0-catalyzed Regio- and Stereoselective Coupling Reaction of Me3B, Isoprene, and Aromatic Aldehydes"Tetrahedron Lett.. 41. 6789-6793 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Shibata, M. Kimura. K. Kojima, S. Tanaka, Y Tamara: "Nickel- catalyzed three-component connection reaction of a phenyl group, conjugated dienes, and aldehydes: stereoselective synthesis of (E)-5-phenyl-3-penten-l-ols and (E)-3-methyl-5-phenyl-3-penten-1-ols"J. Organometal. Chem.. 624. 348-353 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y Horino, M. Naito, M. Kimura, S. Tanaka, Y. Tamara: "Et3B-promoted, Pd-catalyzed C-allylation of o-Hydroxyacetophenone and its derivatives with allyl alcohols"Tetrahedron Latt.. 42. 3113-3116 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Shibata, M. Kimura M. Shimizu, Y. Tamara: "Nickel-Catalyzed Intramolecular Homoallylation of w-Dienyl Aldehyde"Org. Lett.. 3. 2181-2183 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Naito, A. Ezoe, M. Kimura, Y Tamara: "Practical Synthesis of Myrcene Derivatives Possessing Oxidized Methyl Groups"J. Org. Chem. 66. 4447-4449 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kimura, A. Ezoe, S. Tanaka, Y Tamara,: "Nickel-catalyzed homoallylation of Aldehyde in the Presence of Water and Alcohols"Angew. Chem. Int. Ed.,. 40. 3600-3602 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kimura Y. Horino, R. Mukai, S. Tanaka, Y Tamaru: "Strikingly Simple Direct α-Allylation of Aldehydes with Allyl Alcohol: Remarkable Advance in the Tsuji-Trost Reaction"J. Am. Chem. Soc. 123, 10401 (2001). 123. -10401 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ezoe, M. Kimura, T. Inoue, M. Mori, Y. Tamaru: "Remarkably High 1,5-Asymmetric Induction in a Nickel-Catalyzed Through Space Conjugative Addition of Me2Zn and Carbonyls across 1, ω-dienynes"Anew. Chem. Int. Ed.. 41. 2784-2786 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masanari Kimura, Makoto Futamata, Kazufumi Shibata and Yoshinao Tamaru: "Pd-Et_3B Catalyzed Alkylation of Amines with Allylic Alcohols"Chem. Commun.. 124-126 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshikazu Horino, Masanari Kimura, Shuji Tanaka, Toshiya Okajima Yoshinao Tamaru: "Preparation, Structure, and Unique Thermal [2 + 2], [4 + 2], and [3 + 2] Cycloaddition Reactions of 4- Vinylidene-2-oxazolidinone"Chem. Eur. J.. in press. (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masanari Kimura, Masamichi Shimizu, Kazufumi Shibata. Minoru Tazoe, Yoshinao Tamaru: "Pd-catalyzed Nucleophilic Alkylation of Aliphatic Aldehydes with Allyl Alcohols: Allyl, 2-Tetrahydrofuryl and 2-Tetrahydmpyranyl Ethers as Useful 3-, 4-, and 5-Carbon Resources"Angew. Chem. Int. Ed.. in press. (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 木村正成 他 3名: "Ni(0)-Catalyzed Three-Component Connection Reaction of Dimethylzinc, 1,3-Dienes, and Carbonyl Compounds"Angew. Chem. Int. Ed.. 38. 3386-3388 (1999)

    • Related Report
      2002 Annual Research Report
  • [Publications] 木村正成 他 5名: "Nickel-Catalyzed Homoallylation of Aldehydes and Ketones with 1,3-Dienes and Complementary Promotion by Diethylzinc and Triethylborane"Angew. Chem. Int. Ed.. 38. 397-400 (1999)

    • Related Report
      2002 Annual Research Report
  • [Publications] 柴田和文 他 3名: "Nickel-Catalyzed Intramolecular Homoallylation of ω-Dienyl Aldehyde"Org. Lett.. 3. 2181-2183 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] 木村正成 他 3名: "Nickel-catalyzed homoallylation of Aldehyde in the Presence of Water and Alcohols"Angew. Chem. Int. Ed.. 40. 3600-3602 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] 木村正成 他 4名: "Strikingly Simple Direct α-Allylation of Aldehydes with Allyl Alcohol : Remarkable Advance in the Tsuji-Trost Reaction"J. Am. Chem. Soc.. 123. 10401-10402 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] 江副昭宏 他 4名: "Remarkably High 1,5-Asymmetric Induction in a Nickel-Catalyzed Through Space Conjugative Addition of Me2Zn and Carbonyls across 1,ω-dienynes"Anew. Chem Int. Ed.. 41. 2784-2786 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 田丸良直: "Palladium-Catalyzed Reaction of Allyl and Related Derivatives with Organoelectrophiles in Handbook of Organopalladium Chemistry for Organic Synthesis, E.Negishi, Ed"Wiley. 123 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 柴田 和文: "Nickel-catalyzed three-component connection reaction of a phenyl group, conjugated dienes, and aldehydes : stereoselective synthesis of (E)-5-phenyl-3-penten-1-ols"J Organimet. chem.. 624. 348-353 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 堀野良和: "Et3B-promoted, Pd-catalyzed C-allylation of o-hydroxyacetophenone and its derivatives with allyl alcohols"Tetrahedron Lett. 42. 3113-3116 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 柴田和文: "Nickel-Catalyzed Intramolecular Homoallylation of ω-Dienyl Aldehyde"Org. Lett.. 3. 2181-2183 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 内藤 誠: "Practical Synthesis of Myrcene Derivatives Possessing Oxidized Methyl Groups"J. Org. Chem. 66. 4447-4449 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 木村正成: "Nickel-catalyzed homoallylation of Aldehyde in the Presence of Water and Alcohols"Angeu Chem Int. Ed. Engl. 40. 3600-3602 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 木村正成: "Strikingly Simple Direct α-Allylation of Aldehydes with Allyl Alcohol : Remarkable Advance in the Tsuji-Trost Reaction"J. Am. Chem. Soc.. 123. 10401-10402 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 堀野良和: "Novel 1,3-Sulfonyl Shift and [4+2] Cycloaddition Reaction of N-Allenyl Sulfonamide Promoted by Allylsilane"Tetrahedron Lett.. 41. 3427-3431 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 木村正成: "Et_3B-Pd-promoted Allylation of Benzaldehyde with Allylic Alcohols"Tetrahedron Lett.. 41. 3627-3629 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 田丸良直: "Et_3B-promoted, Pd(0)-catalyzed Allylation of Active Methylene Compounds with Allylic Alcohols"Tetrahedron Lett.. 41. 5705-5709 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 木村正成: "Ni(0)-catalyzed Regio- and Stereoselective Coupling Reaction of Me_3B, Isoprene, and Aromatic Aldehydes"Tetrahedron Lett.. 41. 6789-6793 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 柴田和文: "Nickel-catalyzed three-component connection reaction of a phenyl group, conjugated dienes, and aldehydes"J.Organometal, Chem.. (印刷中). (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 根岸英一: "Palladium Handbook"Wiley(印刷中). (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 堀野良和: "Efficient Entry to Tetrahydropyridines: Addition of Enol Ethers to Allene Sulfonamides Invoiving a Novel 1,3-Sultfonyl Shift"Angew.Chem.Int.Ed.Eng.. 38. 121-123 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 木村正成: "Nickel-Catalyzed Homoallylation of Aldehydes and Ketones with 1,3-Dienes and Complementary Promotion by Diethylzinc and Triethytborane"Angew.Chem.Int.Ed.Eng.. 38. 397-400 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 木村正成: "Ni(O)-Catalyzed Three-Component Connection Reaction of Dimethylzinc,1,3-Dienes,and Carbonyl Compounds"Angew.Chem.Int.Ed.Eng.. 38. 3386-3388 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 木村正成: "Palladium-Catalyzed Allylation of Aldehydes via Umpolung of π-Ally]palladium by Triethy lborane"Tetrahedron Lett.. 40. 6795-6798 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 辻二郎(編): "Perspectives in Organopalladium Chemistry for the XXI Century"Elsevier Science. 323 (1999)

    • Related Report
      1999 Annual Research Report

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

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