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Design of Synthetic Intermediates and Elucidation of the Mechanism of Molecular Recognition Based on Computational Calculation

Research Project

Project/Area Number 02453084
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionTokyo Institute of Technology

Principal Investigator

TAKAHASHI Takashi  Tokyo Institute of Technology, Department of Chemical Engineering, Associate Professor., 工学部, 助教授 (80110724)

Co-Investigator(Kenkyū-buntansha) YAMADA Haruo  Tokyo Institute of Technology, Department of Chemical Engineering, Associate Pro, 工学部, 助手 (10175664)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1991: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1990: ¥4,700,000 (Direct Cost: ¥4,700,000)
KeywordsNeocarzinostatin Chromophore / Sarcophytol A / Protonation of the enolate / Transannular Diels-Alder reaction / Molecular mechanics / MM2 transition structure model / Conformational search / 中・大員環エノラ-ト / βー脱離反応 / ab initioーMM2遷移状態モデル / ジアニオン / NCS クロモフォア / ビラジカル / [2,3]ーWittig転位 / ペリプラノンJ.
Research Abstract

The objective of our research is to develop the suitable methods of calculations for the prediction (or analysis) of stereoselectivities in organic reactions and for designing of rational synthetic key intermediates. The methods such as molecular mechanics calculations including the systematic and/or random Monte Carlo conformational searches of synthetic intermediates and MM2 transition structure models for the protonation of the enolates, [2, 3]-Wittig rearrangement and Diels-Alder reaction were examined and found to be useful for this purpose.
We applied these methods to the following synthetic studies. 1)Synthesis of the highly strained bicyclo[7.3.0]diyne skeleton of neocarzinostatin chromophore using transannular[2, 3]-Wittig rearrangement of the 12-membered cyclic ether was achieved. The mechanistic investigations of Meyer's type transannular cyclization of 1 and Bergman cyclization of 2 were undertaken to generate the biradical species. 2)Total synthesis of sarcophytol A 3 which inhibits tumor promotion by teleocidin in two-stage carcinogenesis in mouse skin, was carried out based on the beta-elimination of the enolates on large membered ring system. 3)Synthesis of trans-hydrindanone 4 by conjugate addition-enolate protonation of the 3-alkyl-2-methyl-1-acetylcyclopentenone was examined. 4)Stereoselective transannular Diels-Alder reaction of 5 was examined to develop the general synthetic strategy for the tricyclic compounds. These types of so called "Prediction and Synthesis", where the theoretical calculations are validated by experimental results, are important for the development of the new synthetic strategies.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] Takashi Takahashi: "Synthesis and Transannular Cyclization of Neo-carzinostatin-Chromophore and Esperamici-Calichemicin Analogues" Journal of Organic Chemistry. 56. 3465-3467 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Synthetic Approach to Identification of Periplaneta Sex Pheromones" Tetrahedron Letters. 33. 369-372 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Synthesis and Structural Determination of Periplanone A Based on Molecular Mechanics Calculation" Natural Product Letters.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Macroring Contraction Methodology 6.Transannular Diels-Alder Reaction of the 14-Membered (E,E,E)-Trienone"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Enolate Reactions on Macrocyclic Ring Systems Total Synthesis of (+/-)-Sarcophytol A"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Dianion Methodology for the Construction of Medium-and Large-Mebered Ring Systems:Its Application to the Synthesis of Muscone."

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Studies in Natural Products Chemistry,Stereoselective Synthesis (part E)" Elsevier, (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takayuki Doi, Takashi Takahashi: "Syntheses and Transannular Cyclizations of Neocarzinostatin-Chromo-phore and Esperamicin-Calichemicin Analogues." J. Org. Chem.56. 3465-3467 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi, Takeo Harada, Syozou Takahashi: "Synthetic Approach to Indentification of Periplanneta Sexpheromone." Tetrahedron Lett.33. 369-372 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi, Takeo Harada, Takayuki Doi: "Synthesis and Structure Determination of Periplanone A Based on Molecular Mechanics Calculation." Natural Products Letters.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi, Yasuharu Sakamoto, Takayuki Doi: "Macroring Constraction Methodology 6. Transannular Diels-Alder Reaction of the 14-Membered (E, E, E) -trienones."

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi, Hajime Yakoyama, Takeharu Haino, Haruo Yamada: "Enolate Reactions on Macrocyclic Ring systems. Total Synthesis of (+__-) -Sarcophytol A." J. Org. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi, Haruo Yamada, Takaharu Haino, Yoichi Kido, Yoshimasa Fukazawa: "Dianion Methodology for the Construction of Medium- and Large-Membered Ring Systems : It's application to the Synthesis of Muscone."

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: " "Natural Products Syntheses by Using Macrocyclically Controlled Reactions" in "Studies in Natural Products Chemistry" , Stereoselective Synthesis (Part E)" Elsevier, Amsterdam. 8. 175-204 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Takashi Takahashi: "Synthesis and Transannular Cyclization of NeoーcarzinostatinーChromophore and EsperamicinーCalichemicin Analogues" Journal of Organic Chemistry. 56. 3465-3467 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Takashi Takahashi: "Synthetic Approach to Identification of Periplaneta Sex Pheromones" Tetrahedron Letters. 33. 369-372 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Takashi Takahashi: "Synthesis and Structural Determination of Periplanone A Based on Molecular Mechanics Calculation" Natural Product Letters.

    • Related Report
      1991 Annual Research Report
  • [Publications] Takashi Takahashi: "Macroring Contraction Methodology 6.Transannular DielsーAlder Reaction of the 14ーMembered(E,E,E)ーTrienone"

    • Related Report
      1991 Annual Research Report
  • [Publications] Takashi Takahashi: "Enolata Reactions on Macrocyclic Ring Systems Total Synthesis of(+/-)-Sarcophytol A"

    • Related Report
      1991 Annual Research Report
  • [Publications] Takashi Takahashi: "Dianion Methodology for the Construction of Mediumーand LargeーMembered Ring Systems: Its Application to the Synthesis of Muscone."

    • Related Report
      1991 Annual Research Report
  • [Publications] Takashi Takahashi: "Studies in Natural Products Chemistry,Stereoselective Synthesis(part E)" Elsevier, (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Takayuki Doi: "Synthesis and Transannvlar Cyclization of Neocarzinostatin Chromophore and EsperamicinーCalichemicin Analogs" J.Org.Chem.

    • Related Report
      1990 Annual Research Report
  • [Publications] 山田 晴夫: "有機合成の新手段ーコンピュ-タの活用ー" 有機合成化学協会誌. 48. 593-605 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 高橋 孝志: "ペリプラノンA.B.Jの分子力場計算に基づく合成及びその生理活性" 第57回 有機合成シンポジウム講演要旨集. 56-59 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Haruo Yamada.: "New Synthetic Intermediate for Transー8ーmethylhydrindanones." Tetrahedron Lett.,. 31. 2407-2410 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Takashi Takahashi: "Diastereo and Enantioselective Transannvlar DielsーAlder Reactions of 14 membered Enones."

    • Related Report
      1990 Annual Research Report
  • [Publications] Haruo Yamada.: "Efficient Cyclization of 14,18ーmembered Rings by Means of Dianions."

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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