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2002 Fiscal Year Final Research Report Summary

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
Keywordspalladium / triethlylborane / diethylzinc / allyl alcohol / allylation / alkylation / H2O tolerance / amphiphillic activation / environment / aldehyde
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.

  • Research Products

    (22 results)

All Other

All Publications (22 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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)

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      「研究成果報告書概要(欧文)」より
  • [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)

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      「研究成果報告書概要(欧文)」より
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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)

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  • [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)

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Published: 2004-04-14  

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