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分子認識場の設計

Research Project

Project/Area Number 02230106
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionKyushu University

Principal Investigator

新海 征治  九州大学, 工学部, 教授 (20038045)

Co-Investigator(Kenkyū-buntansha) 戸田 芙三夫  愛媛大学, 工学部, 教授 (50036232)
古賀 憲司  東京大学, 薬学部, 教授 (10012600)
笠井 暢民  大阪大学, 工学部, 教授 (50028958)
岡原 光男  大阪大学, 工学部, 教授 (70028992)
稲津 孝彦  九州大学, 理学部, 教授 (60037207)
Project Period (FY) 1989 – 1991
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥30,600,000 (Direct Cost: ¥30,600,000)
Fiscal Year 1990: ¥30,600,000 (Direct Cost: ¥30,600,000)
Keywordsカリックスアレ-ン / デオキシコ-ル酸 / クラウンエ-テル / シクロファン / 分子認識 / イオン輸送 / 包接化合物 / 光学分割
Research Abstract

本年度は新しい分子認識場を設計するとともに、その認識精度の向上および動的側面について研究を遂行した。水溶性カリックスアレ-ンのゲスト分子包接錯体の構造がX線により初めて解析された。また、分子不斉要素をもつ光学活性カリックスアレ-ンが合成され、光学分割された(新海)。デオキシコ-ル酸の環状三量体が提供する空孔は、分子包接能を示す新しいホスト化合物として作用することが判明した。その包接挙動を種々のスペクトル的手法を駆使して明らかにした(稲津)。アルカリ金属イオンを選択的に取に込むクラウンエ-テルに配位性の側鎖を導入することにより、会合性,選択性とも向上することが明らかになった。さらに、Na^+とK^+選択性を示す2個のクラウン環を同一分子内に持つビスクラウンエ-テルは液体膜系でNa^+とK^+の対向輸送能力を持つことが明らかとなった(岡原)。包接現象を示すホスト化合物は特異な空孔をもつ結晶構造を取ることが明らかとなりつつある。特に、水素結合や双極子相互作用が支配的な要因として働く。コンホメ-ション異性を示す環状化合物は、結晶構造やゲスト分子の有無により異なる形を取ることがX線結晶解析の結果明らかとなった(笠井)。ジアリ-ルメタン骨格を有する水溶性のシクロファンは秀れたホスト化合物として働き,特にアリ-ル基上に導入した電荷により、ゲスト分子を識別する能力を示すことが解った(古賀)。ゲスト分子の大きさに対応して認識能を発揮する非環状ホスト化合物が設計された。その結晶場を利用して、反応の立体規制を固相で行うことが可能となった(戸田)。
以上の結果として、分子認識場の設計と評価および選択的反応場としての利用が可能となった。

Report

(1 results)
  • 1990 Annual Research Report
  • Research Products

    (59 results)

All Other

All Publications (59 results)

  • [Publications] A.Yamada: "NMR Relaxation Time Studies of Ionophoric Calixarene Esters" Chem.Lett.455-458 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Synthesis and Inclusion Properties of “Neutral WaterーSoluble Calixarenes" Bull.Chem.Soc.Jpn.63. 1272-1274 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Metal Selectivity of Conformational Isomers Derived from pーtーButylcalix[4]arene" Chem.Lett.835-838 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] O.Manabe: "DiazoーCoupling with a ResocinolーBased Cyclophane.A New WaterーSoluble Host with a Deep Cleft" Chem.Lett.1219-1222 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "“Cone"ー“Partial Cone" Isomerism in Tetramethoxyーpーtーbutylcalix[4]arene.Novel Solvent Effects and Metal Template Effects" Chem.Lett.1263-1266 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Iwamoto: "Synthesis and Optical Resolution of a Chiral Calix[4]arene AsymmetricallyーSubstituted on the Lower Rim" Chem.Lett. 1901-1904 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Nagaski: "Synthesis and Solvent Extraction Properties of a Novel CalixareneーBased Uranophile Bearing Hydroxamate Groups" J.Chem.Soc.,Perkin Trans.1. 2617-2818 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "NMR and Crystallographic Studies of a pーSulfonatoーCalix[4]areneーGuest Complex" J.Am.Chem.Soc.112. 9053-9058 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Araki: "“pK_a" of Calixarenes and Analogs in Nonaqueous Solvents" Bull.Chem.Soc.Jpn.63. 3480-3485 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "A Photochemically Activated Cyclophane" J.Chem.Soc.,Perkin Trans.2. 1905-1909 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Synthesis and Optical Resolution of an Asymmetrically Substituted Calix[4]arene" J.Chem.Soc.,Chem.Commun.1734-1736 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Iwamoto: "Remarkable Metal Template Effects on Selective Syntheses of pーtーButylcalix[4]arene Conformers" Tetrahedron Lett.31. 7169-7172 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Katsuya Sako: "Conformational Analysis of [3.3]Paracyclophane" Chem.Ber.123. 639-642 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Tatsuya Meno: "Conformational Analysis of [3.3.3](1,3,5)Cyclophane Systems" Can.J.Chem.68. 440-445 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yuji Miyahara: "An Extremely Efficient Synthesis of Thiophene 1,1ーDioxides.Oxidation of Thiophene Derivatives with Dimethyldioxirane" Tetrahedron Lett.31. 5955-5958 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Hiroyuki Takemura: "Syntheses and Properties of Highly Symmetrical Cage Compounds:Pyridine Analogs of “Hexametaxylyleneーtetraamine"" J.Am.Chem.Soc.

    • Related Report
      1990 Annual Research Report
  • [Publications] Ryuhei Wakita: "CーPivot Lariat Ethers Bearing an ElectonーDonating Side Arm as Li^+ Selective Extractants" J.Org.Chem.55. 2752-2756 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Ryuhei Wakita: "Synthesis of Methylーsubstituted Lariat Ethers Containing a 13ーCrownー4 Ring" J.Heterocyclic Chem.27. 1337-1339 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Miki: "Crystal Structure of Cholic Acid with No Guest Molecules" Acta Cryst.C46. 2442-2445 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Kaida: "Structure of Iminodiacetonitrile" Acta Cryst.C46. 2269-2270 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] N.Kanehisa: "Facile Synthesis of Group 4ー6 Transition Metal Phenoxided and Xーray Structures of TiCl_2[Oー2,6ー(CH_3)_2C_6H_3]_2(THF)_2 and NbCl_3[Oー2,6ー(CH_3)_2C_6H_3]_2(THF)" Chem.Lett.2167-2170 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Iyoda: "Thermal and Nickelーcatalyzed Dimerization of Hexapentaene.Synthesis of Two [4]Radialenes with Planar,Stable Cyclobutadieneーlike Geometry" Chem.Lett.2149-2152 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Iyoda: "NickelーCatalyzed Cyclodimerization of Hexapentanes:[4]Radialenes and [5]Radialenones with Cumulated Double Bonds" Angew.Chem.Int.Ed.Engl.29. 1062-1063 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] R.Wakita: "Synthesis and NーAlkylation of 5ーBromomethylー5ーmethylー1,4,7,10ーtetraoxaー13ーazacyclopentadecane" Synthesis. 1011-1012 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 古賀 憲司: "超分子の化学" 化学. 45. 618-619 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Sasaki,Y.Takase,K.Koga: "An Attempt on Acceleration of Peptide Synthesis Using the Enzyme model Having preorganized Catalytic Groups" Tetrahedron Letters. 31. 6051-6054 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Yasukata,S.Sasaki,K.Koga: "Novel Bicyclic Chiral Crown Ethers Having pーXylenedioxy Unit with Improved Complex Stability and Rateーenhancement in the Intracomplex Thiolysis of Amino Acid Ester Salts" Chem.Pharm.Bull.39. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Absolute StructureーCytotoxic Activity Relationship of Steganacin Congeners and Analogs" J.Med.Chem.34. 54-57 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Tomioka,I.Inoue,M.Shindo,K.Koga: "Asymmetric Organolithium Additions to Imines" Tetrahedron Letters. 31. 6681-6684 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Stereoselective Reactions.XIX.Asymmetric Dihydroxylation of Olefins by Employing Osmium TetroxideーChiral Amine Complexes" Chem.Pharm.Bull.38. 2133-2135 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Stereoselective Reactions.XVIII.Synthesis and Cytotoxicity of the Demethyl Derivatives of Stegans" Chem.Pharm.Bull.38. 1899-1901 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Regioselective Enolization of Optically Active 3ーKeto Steroids Using Chiral Lithium Amides" Tetrahedron:Asymmetry. 1. 295-298 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga: "Enantioselective Reactions Using Chiral Lithium Amides" J.Synth.Org.Chem.,Jpn.48. 463-475 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Reductive Generation of Aldehyde Metal Enolate from Ketene.A OneーFlaks Process to 1,1,2ー and 1,2,2ーTrisubstituted Dihydronaphthalenes from 1ー and 2ーNaphthlenecarboxylates" J.Org.Chem.55. 2276-2277 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Dramatic Enantioselectivity Change in Dihydroxylation of Olefins with Chiral AmineーOsmium Tetroxide Complex" Tetrahedron Letters. 31. 1741-1742 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Koga,et al: "Conjugate Addition Reaction of Organolithiums to Naphthalenecarboxylates" Tetrahedron Letters. 31. 1739-1740 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Fujiwara,N.Tanaka,R.Ooshita,R.Hino,K.Mori,and F.Toda: "Crystal and Molecular Structure of the Crystalline HostーGuest Complex between (R)ー(+)ー2,2'ーDihydroxyー1,1'ーbinaphthyl and (S)ー(ー)ー(Ethyl mーTolyl Selenoxide)" Bull.Chem.Soc.Jpn.63. 249-251 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,Y.Kagawa,and Y.Sakaino: "Benzylic Acid Rearrangement in the Solid State" Chem.Lett.373-376 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,and M.Yagi: "New Preparative and Optical Resolution Method of βーLactams" J.Chem.Soc.,Perkin Trans.1. 1215-1216 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Tanaka,S.Kishigami,and F.Toda: "A New Method for Coupling Aromatic Aldehydes and Ketones To Produce αーGlycols Using ZnーZnCl_2 in Aqueous Solution and in the Solid State" J.Org.Chem.55. 2981-2983 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda and H.Akai: "Enantioselective WittigーHorner Reaction in the Solid State" J.Org.Chem.55. 3446-3447 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda and Y.Tokumaru: "Oxidative Coupling Reaction of Acetylenic Compounds in the Solid State" Chem.Lett.987-990 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda and K.Tanaka: "Guest(Solvent)ーDependent Enantioselective Crystallization of 7ーBromoー1,4,8ーtripheny1ー2,3ーbenzo[3.3.0]octaー2,4,7ーtrienー6ーonr" Tetrahedron Assym.359-362 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Kishigami,K.Tanaka,and F.Toda: "A New Preparative Method of Butaー1,3ーdiene and Hexaー1,5ーdienー3ーyne by Reduction of Butatriene and Hexapentaene,Respectively,with ZnーZnCl_2ーH_2O" Chem.Lett.1877-1880 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Todam H.Takumi,and M.Akehi: "Efficient Solidーstate Reaction of Alcohols:Dehydration,Rearrangement,and SUbstitution" J.Chem.Soc.,Chem.Commun.1270-1271 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,and K.Hamai: "Aldol Condensation in the Absence of Solvent:Acceleration of the Reaction and Enhancement of the Stereochemistry" J.Chem.Soc.,Perkin Trans.1. 3207-3209 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda,K.Mori,Y.Matsuura,and H.Akai: "Solid State Kinetic Resolution of βーIonone Epoxide and Dialkyl Sulphoxides in the Presence of Optically Active Host Compounds." J.Chem.Soc.,Chem.Commun.1591-1593 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda: "Selective Reactions in the Solid State and Organic SolidーSolid Reactions" Mol.Cryst.Liq.Cryst.187. 41-48 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Mori and F.Toda: "Optical Resolution of Arsine Oxides by Complexation with Optically Active [1,1'ーBinaphthyl]ー2,2'ーdiol" Bull.Chem.Soc.Jpn.63. 2127-2128 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Mori and F.Toda: "Efficient Optical Resolution of Aziridines by Complexation with Optically Active Host Compounds" Tetrahedron Assym.281-282 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda,R.Toyotaka,and H.Fukuda: "Optically Active 4,4'6,6'ーTetrachloroー2,2'ーbis(hydroxydiphenylmethyl)biphenyl As a Host for Optical Resolution and a Chiral Shift Reagent" Tetrahedron Assym.303-306 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,and T.Fujiwara: "Isolation of Conformational Isomers of αー and βーIonones by Inclusion Complex Formation" Angew.Chem.Int.Ed.Engl.29. 662-664 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Fujiwara,N.Namba,K.Hamada,F.Toda,and K.Tanaka: "Enantioselective Photoreactions of Cyclooctaー2,4,6ーtrienー1ーone and Cyclooctaー2,4ーdienー1ーone in Their Inclusion Complexes with (R,R)ー(ー)ーBis(oーchlorophenyl)hexadinediol" J.Org.Chem.55. 4532-4537 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda and H.Akai: "Isolation of Optically Active Oximes" J.Org.Chem.55. 4973-4974 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Liquid Membranes:Chemical Applications" CRC Press, 14 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Bioorganic Chemistry Frontiers" Springer Verlag, 34 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Cation Binding by Macrocycles" Marcel Dekker, 31 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Shinkai: "Inclusion Phenomena and Molecular Recognition" Plenum Publishing Co., 8 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] F.Toda: "Future Opportunities in Catalytic and Separation Technology" Elsevier, 381 (1990)

    • Related Report
      1990 Annual Research Report

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

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