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1991 Fiscal Year Final Research Report Summary

Circular Dichroism of Twisted pi-Electron Systems and Its Application to Natural Products Chemistry

Research Project

Project/Area Number 01470026
Research Category

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

Allocation TypeSingle-year Grants
Research Field 天然物有機化学
Research InstitutionTohoku University

Principal Investigator

HARADA Nobuyuki  Tohoku University, Institute for Chemical Reaction Science Associate Professor, 反応化学研究所, 助教授 (30006324)

Project Period (FY) 1989 – 1991
KeywordsCD exciton chirality method / twisted pi-electron system / absolute stereochemistry / absolute stereochemistry of acyclic glycols / cardiotonic marine natural product / natural atropisomer biflavone / phototropism-regulating substances / AChE activity inhibitor
Research Abstract

The CD spectroscopic method is useful for non-empirical determination of the absolute configuration of chiral organic compounds, in addition to the X-ray method. We have developed the new theoretical method for determination of the absolute stereochemistry of twisted pi-electron systems, and have applied it to the natural products chemistry.
(1) Efficient preparation of optically pure Wieland-Miescher ketone and confirmation of its absolute stereochemistry by the CD exciton chirality method.
(2) Crystalline structure and absolute stereochemistry of chloromonilicin, a growth selfinhibitor produced by Monilinia fructicola, determined by X-ray and CD methods.
(3) Total synthesis of (+)-xestoquinone, an cardiotonic marine natural product, and determination of its absolute stereochemistry.
(4) Synthesis, CD, and absolute stereochemistry of optically active 9, 9'-spirobifluorene and[6, 6]-vespirene derivatives with polyscene chromophores.
(5) Synthesis of chiral spiro[3.3]heptane compounds and de … More termination of their absolute configuration by application of the CD exciton chirality method.
(6) Synthesis, absolute stereochemistry, and isolation of (+)-prehalenaquinone, a putative biosynthetic precursor common to halenaquinone and xestoquinone compounds.
(7) Determination of the absolute stereochemistry of[6, 6]-vespirene derivatives by the X-ray method.
(8) A CD method for determination of the absolute stereochemistry of acyclic glycols.
(9) Absolute stereochemistry of natural atropisomer biflavone as determined by the theoretical calculation of CD spectra.
(10) Unique ultraviolet-visible and circular dichroism behavior due to exciton coupling in a biscyanine dye.
(11) Optical resolution of carboxylic acids by use of (-)-sultam and determination of absolute configuration.
(12) Determination of the absolute stereochemistry of cyclophanes by the X-ray methods.
(13) Revision of the structure of raphanusanins, phototropism-regulating substances of radish hypocotyls, and biological activity of raphanusanin analogus.
(14) Structure of NK901093, an AChE activity inhibitor produced by Streptomyces lavendulae. Less

  • Research Products

    (52 results)

All Other

All Publications (52 results)

  • [Publications] N.Harada: "Circular Dichroic Power of Chiral Spiro Aromatics.Theoretical Calculation of the CD and UV Spectra of 2,2'-Spirobi[2H-benz[e]indene] Derivatives" Croatica Chemica Acta. 62. 267-278 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Interchromophoric Homoconjugation Effect and Intramolecular Charge-transfer Transition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore" Journal of the Chemical Society,Perkin Transaction II. 1449-1453 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Synthesis,Absolute Stereochemistry,and Circular Dichroism of Chiral 1,8a-Dihydroazulene Derivatives" Journal of Organic Chemistry. 54. 1820-1826 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Absolute Stereochemistry of the Halenaquinol Family,Marine Natural Products with a Novel Pentacyclic Skeleton,As Determined by the Theoretical Calculation of Circular Dichroism Spectra" Jounal of the American Chemical Society. 111. 5668-5674 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Efficient Preparation of Optically Pure Wieland-Miescher Ketone and Confirmation of Its Absolute Stereochemistry by the CD Exciton Chirality Method" Synthesis. 53-56 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Total Synthesis and Absolute Stereochemistry of(+)-Xestoquinone and Xestoquinol" Journal of Organic Chemistry. 55. 3158-3163 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols.1.Application of the CD Exciton Chirality Method to Acyclic 1.3-Dibenzoate Systems" Journal of the American Chemical Society. 113. 3842-3850 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Suzuki: "Enantioselective Synthesis of the AB Ring Fragment of Gambiertoxin 4B.Implication for the Absolute Configuration of Gambiertoxin 4B and Ciguatoxin" Tetrahedron Letters. 32. 4505-4508 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] D.Gargiulo: "Unique Ultraviolet-Visible and Circular Dichroism Behavior Due to Exciton Coupling in a Biscyanine Dye" Journal of the American Chemical Society. 113. 7046-7047 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Revision of the Structure of Raphanusanins,Phototropism-Regulating Substances of Radish Hypocotyls" Tetrahedron Letters. 32. 6757-6760 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Revision of the Structure of Raphanusamide,a Phototropism-Regulating Substance of Radish Hypocotyls" Tetrahedron Letters. 32. 6761-6762 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Synthesis,Circular Dichroism and Absolute Stereochemistry of Chiral Spiroaromatic Compounds.9,9'-Spirobifluorene Derivatives" Journal of the Chemical Society,Chemical Communication. 1753-1755 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Absolute Stereochemistry of (-)-Wieland-Miescher Ketone as Established by the X-Ray Crystallographic and CD Exciton Chirality Methods" Collection of Czechoslovak Chemical Communications. 57. (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Lourenco: "The Absolute Stereochemistry at C-12 in 12-Hydroxylate Neo-Clerodane Diterpenoids" (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Atropisomerism in Natural Products.Absolute Stereochemistry of Biflavone,(-)-4',4''',7,7''-Tetra-O-methylcupressuflavone,as Determined by the Theoretical Calculation of CD Spectra" (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols.2.Application of the CD Exciton Chirality Method to Acyclic 1,2-Dibenzoate Systems" (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Synthesis,Absolute Stereochemistry,and Isolation of(+)-Prehalenaquinone,a Putative Biosynthetic Precursor Common to Halenaquinone and Xestoquinone Compounds" (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Synthesis,Circular Dichroism,and Absolute Stereochemistry of Chiral Spiro[3.3]heptane Derivatives" (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Circular Dichroism of Twisted π-Electron Systems:Absolute Stereochemistry of the Halenaquinol Family and Total Synthesis of Optically Active Members" Petr Malon and Petr Pancoska,Ed.,Proceedings of the Third International Conference on CD Spectroscopy,Prague,Czechoslovakia, 15 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Circular Dichroism and of Absolute Stereochemistry of Optically Active 9,9'-Spirobifluorene Derivatives" Petr Malon and Petr Pancoska,Ed.,Proceedings of the Third International Conference on CD Spectroscopy,Prague,Czechoslovakia, 6 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 原田 宣之: ""旋光性とCDスペクトル"第5章 後藤 俊夫,芝 哲夫,松浦 輝男監修「有機化学実験のてびき」" 化学同人、京都, 18 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 原田 宣之: ""屈折率と旋光度"第3章4節 日本化学会編、「第4版実験化学講座1、基本操作I」" 丸善、東京, 14 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Synthesis,CD Spectra,and Absolute Stereochemistry of Chiral Spiranes" H.Klein and G.Snatzke,Ed.,Proceedings of the Fourth International Conference on CD Spectroscopy,Bochum,Germany, 10 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 原田 宣之: ""円二色性"第4章6節1項 日本化学会編、「第4版実験化学講座7、分光II」" 丸善、東京, 14 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "'Circular Dichroism,Absolute Stereochemistry,and Total Synthesis of Halenaquinol Compounds,Novel Marine Natural Products Isolated from Tropical Sea Sponges',in A.-U.Rahman,Ed.,"Studies in Natural Products Chemistry"" Elsevier Science Publishers,Amsterdam,Netherlands, (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Harada: "Circular Dichroism Spectroscopy,Exciton Coupling in Organic Stereochemistry,Second Edition" University Science Books,California,U.S.A.,and Oxford University Press,Oxford,England, (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N. Harada, J. Iwabuchi, Y. Yokota, and H. Uda.: ""Circular Dichroic Power of Chiral Spiro Aromatics. Theoretical Calculation of the CD and UV Spectra of 2, 2'-Spirobi[2H-benz[e]indene]Derivatives"" Croatica Chemical Acta. 62. 267-278 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, H. Uda, K. Nakasuji, and I. Murata.: ""Interchromophoric Homoconjugation Effect and Intramolecular Charge-transferTransition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore"" J. Chem. Soc., Perkin Trans. II. 1449-1453 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, J. Kohori, H. Uda, and K. Toriumi: ""Synthesis, Absolute Stereochemistry, and Circular Dichroism of Chiral 1, 8a-Dihydroazulene Derivatives"" J. Org. Chem.54. 1820-1826 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, H. Uda, M. Kobayashi, N. Shimizu, and I. Kitagawa.: ""Absolute Stereochemistry of the Helenaquinol Family, Marine Natural Products with Novel Pentacyclic Skeleton, As Determined by the Theoretical Calculation of Circular Dichroism Spectra"" J. Am. Chem. Soc.111. 5668-5674 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, T. Sugioka, H. Uda, and T. Kuriki: ""Efficient Preparation of Optically Pure Wieland-Miescher Ketone and Confirmation of Its Absolute Stereochemistry by the CD Exciton Chirality Method"" Synthesis. 53-56 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, T. Sugioka, H. Uda, and T. Kuriki: ""Total Synthesis and Absolute Stereochemistry of (+)-Xestoquinone and Xestoquinol"" J. Org. Chem.55. 3158-3163 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, A. Saito, H. Ono, J. Gawaronski, Gawronska, T. Sugioka, H. Uda, and T. Kuriki: ""A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols. 1. Application of the CD Exciton Chirality Method to Acyclic 1, 3-Dibenzoate Systems"" J. Am. Chem. Soc.113. 3842-3850 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Suzuki, O. Sato, M. Hirama, Y. Yamamoto, M. Murata, T. Yasumoto, and N. Harada: ""Enantioselective Synthesis of the AB Ring Fragment of Gambiertoxin 4B. Implication for the Absolute Configuration of Gambiertoxin 4B and Ciguatoxin"" Tetrahedron Lett.32. 4505-4508 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] D. Gargiulo, F. Derguini, N. Berova, K. Nakanishi, and N. Harada: ""Unique Ultraviolet-Visible and Circular Dichroism Behavior Due to Exciton Coupling in a Biscyanine Dye"" J. Am. Chem. Soc.113. 7046-7047 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, H. Hagiwara, H. Ono, H. Uda, S. Ohba, M. Kubota, S. Nishiyama, S. Yamamura, K. Hasagawa, and M. Sakoda: ""Revision of the Structure of Raphanusanins, Phototropism-Regulating Substances of Radish Hypocotyls"" Tetrahedron Lett.32. 6757-6760 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, H. Ono, H. Hagiwara, H. Uda, K. Hasegawa, and M. Sakoda: ""Revision of the Structure of Raphanusamide, a Phototropism-Regulating Substances of Radish Hypocotyls"" Tetrahedron Lett.32. 6761-6762 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, H. Ono, T. Nishiwaki, and H. Uda: ""Synthesis, Circular Dichroism and Absolute Stereochemistry of Chiral Spiroaromatic Compounds. 9, 9'-Spirobifluorene Derivatives"" J. Chem. Soc., Chem. Commun.1753-1755 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Haraka, T. Sugioka, H. Uda, and T. Kuriki: ""Absolute Stereochemistry of (-)- Wieland-Miescher Ketone as Established by the X-Ray Crystallographic and CD Exciton Chirality Methods"" Collection of Czechoslovak Chemical Communications. 57. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A. Lourenco, M. C. de la Torre, B. Rodriguez, N. Harada, H. Ono, H. Uda, M. Bruno, F. Piozzi, and G. Savona: ""The Absolute Stereochemistry at C-12 in 12-Hydroxylated Neo-Clerodane Diterpenoids"" Tetrahedron. 48. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, H. Ono, H. Uda, M. Parveen, N. U. -D. Khan, B. Achari, and P. K. Dutta: ""Atropisomerism in Natural Products. Absolute Stereochemistry of Biflavone, (-)-4', 4" , 7, 7"-Tetra-O-methylcupressuflavone, as Determined by the Theoretical Calculation of CD Spectra"" (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, A. Saito, H. Ono, J. Gawronski, K. Gawronska, H. Sato, T. Sugioka, H. Uda, and T. Kuriki: ""A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols. 2. Application of the CD Exciton Chirality Method to Acyclic 1, 2-Dibenzoate Systems"" (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, T. Sugioka, H. Uda, T. Kuriki, M. Kobayashi, and I. Kitagawa: ""Synthesis, Absolute Stereochemistry, and Isolation of (+)-Prehalenaquinone, a Putative Biosynthetic Precursor Common to Halenaquinone and Xestoquinone Compounds"" (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, S. Murai, T. Soutome, and H. Uda: ""Synthesis, Circular Dichroism, and Absolute Stereochemistry of Chiral Spiro[3.3]heptane Derivatives""

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada: ""Ciroular Dichroism of Twisted pi-Electron Systems : Absolute Stereochemistry of the Halenaquinol Family and Total Synthesis of Optically Active Members"" Proceedings of the Third International Conference of CD Spectroscopy. Prague, Czechoslovakia. 1-15 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Haraka, T. Nishiwaki, H. Ono, and H. Uda.: ""Circular Dichroism and of Abusolute Stereochmistry of Optically Active 9, 9'-Spirobifluorene Derivatives"" Proceedings of the Third International Conference on CD Spectroscopy. Prague, Czechoslovakia. 1989 (155-160)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada: ""Optical Rotation and CD Spectroscopy", Chapter 5" Yuuki Kagaku Jikken no Tebiki'. Kagaku Dojin. 85-102 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada: ""Refractive Index and Optical Rotation", Chapter 3, Section 4," 'Dai-4-han Jikken Kagaku Koza 1, Kohon Sousa I'. Maruzen. 91-104 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada: ""Synthesis, CD Spectra, and Absolute Stereochemistry of Chiral Spiranes"" Proceeding of the Fourth International Conference on CD Spectroscopy. Bochum. 202-211 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada: ""Circular Dichroism", Chapter 4, Section 6-1," Dai-4-han Jikken Kagaku Koza 7, Bunkou II'. Maruzen. 254-266 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada: ""Circular Dichroism, Absolute Stereochemistry, and Total Synthesis of Halenaquinol Compounds, Novel Marine Natural Products Isolated form Tropical Sea Sponges"" 'Studies in Natural Products Chemistry'. Elsevier Science Publishers. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Harada, N. Berova, and K. Nakanishi: ""Circular Dichroism spectroscopy-Exciton coupling in Organic Stereochemistry-", Second Edition" University Science Books. Mill Valley, California and Oxford University Press. (1992)

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

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Published: 1993-03-16  

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