分子認識場の設計

1990 年度 実績報告書

• 研究課題/領域番号: 02230106
• 研究機関: 九州大学
• 研究代表者: 新海 征治 九州大学, 工学部, 教授 (20038045)
• 研究分担者: 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)
• キーワード: 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

研究概要

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。

研究成果

• [文献書誌] A.Yamada: "NMR Relaxation Time Studies of Ionophoric Calixarene Esters" Chem.Lett.455-458 (1990)
• [文献書誌] S.Shinkai: "Synthesis and Inclusion Properties of “Neutral WaterーSoluble Calixarenes" Bull.Chem.Soc.Jpn.63. 1272-1274 (1990)
• [文献書誌] S.Shinkai: "Metal Selectivity of Conformational Isomers Derived from pーtーButylcalix[4]arene" Chem.Lett.835-838 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] K.Iwamoto: "Synthesis and Optical Resolution of a Chiral Calix[4]arene AsymmetricallyーSubstituted on the Lower Rim" Chem.Lett. 1901-1904 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] K.Araki: "“pK_a" of Calixarenes and Analogs in Nonaqueous Solvents" Bull.Chem.Soc.Jpn.63. 3480-3485 (1990)
• [文献書誌] S.Shinkai: "A Photochemically Activated Cyclophane" J.Chem.Soc.,Perkin Trans.2. 1905-1909 (1990)
• [文献書誌] S.Shinkai: "Synthesis and Optical Resolution of an Asymmetrically Substituted Calix[4]arene" J.Chem.Soc.,Chem.Commun.1734-1736 (1990)
• [文献書誌] K.Iwamoto: "Remarkable Metal Template Effects on Selective Syntheses of pーtーButylcalix[4]arene Conformers" Tetrahedron Lett.31. 7169-7172 (1990)
• [文献書誌] Katsuya Sako: "Conformational Analysis of [3.3]Paracyclophane" Chem.Ber.123. 639-642 (1990)
• [文献書誌] Tatsuya Meno: "Conformational Analysis of [3.3.3](1,3,5)Cyclophane Systems" Can.J.Chem.68. 440-445 (1990)
• [文献書誌] Yuji Miyahara: "An Extremely Efficient Synthesis of Thiophene 1,1ーDioxides.Oxidation of Thiophene Derivatives with Dimethyldioxirane" Tetrahedron Lett.31. 5955-5958 (1990)
• [文献書誌] Hiroyuki Takemura: "Syntheses and Properties of Highly Symmetrical Cage Compounds:Pyridine Analogs of “Hexametaxylyleneーtetraamine"" J.Am.Chem.Soc.
• [文献書誌] 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)
• [文献書誌] Ryuhei Wakita: "Synthesis of Methylーsubstituted Lariat Ethers Containing a 13ーCrownー4 Ring" J.Heterocyclic Chem.27. 1337-1339 (1990)
• [文献書誌] K.Miki: "Crystal Structure of Cholic Acid with No Guest Molecules" Acta Cryst.C46. 2442-2445 (1990)
• [文献書誌] S.Kaida: "Structure of Iminodiacetonitrile" Acta Cryst.C46. 2269-2270 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 古賀 憲司: "超分子の化学" 化学. 45. 618-619 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] K.Koga,et al: "Absolute StructureーCytotoxic Activity Relationship of Steganacin Congeners and Analogs" J.Med.Chem.34. 54-57 (1991)
• [文献書誌] K.Tomioka,I.Inoue,M.Shindo,K.Koga: "Asymmetric Organolithium Additions to Imines" Tetrahedron Letters. 31. 6681-6684 (1990)
• [文献書誌] 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)
• [文献書誌] K.Koga,et al: "Stereoselective Reactions.XVIII.Synthesis and Cytotoxicity of the Demethyl Derivatives of Stegans" Chem.Pharm.Bull.38. 1899-1901 (1990)
• [文献書誌] K.Koga,et al: "Regioselective Enolization of Optically Active 3ーKeto Steroids Using Chiral Lithium Amides" Tetrahedron:Asymmetry. 1. 295-298 (1990)
• [文献書誌] K.Koga: "Enantioselective Reactions Using Chiral Lithium Amides" J.Synth.Org.Chem.,Jpn.48. 463-475 (1990)
• [文献書誌] 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)
• [文献書誌] K.Koga,et al: "Dramatic Enantioselectivity Change in Dihydroxylation of Olefins with Chiral AmineーOsmium Tetroxide Complex" Tetrahedron Letters. 31. 1741-1742 (1990)
• [文献書誌] K.Koga,et al: "Conjugate Addition Reaction of Organolithiums to Naphthalenecarboxylates" Tetrahedron Letters. 31. 1739-1740 (1990)
• [文献書誌] 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)
• [文献書誌] F.Toda,K.Tanaka,Y.Kagawa,and Y.Sakaino: "Benzylic Acid Rearrangement in the Solid State" Chem.Lett.373-376 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] F.Toda and H.Akai: "Enantioselective WittigーHorner Reaction in the Solid State" J.Org.Chem.55. 3446-3447 (1990)
• [文献書誌] F.Toda and Y.Tokumaru: "Oxidative Coupling Reaction of Acetylenic Compounds in the Solid State" Chem.Lett.987-990 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] F.Toda: "Selective Reactions in the Solid State and Organic SolidーSolid Reactions" Mol.Cryst.Liq.Cryst.187. 41-48 (1990)
• [文献書誌] 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)
• [文献書誌] K.Mori and F.Toda: "Efficient Optical Resolution of Aziridines by Complexation with Optically Active Host Compounds" Tetrahedron Assym.281-282 (1990)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] 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)
• [文献書誌] F.Toda and H.Akai: "Isolation of Optically Active Oximes" J.Org.Chem.55. 4973-4974 (1990)
• [文献書誌] S.Shinkai: "Liquid Membranes:Chemical Applications" CRC Press, 14 (1990)
• [文献書誌] S.Shinkai: "Bioorganic Chemistry Frontiers" Springer Verlag, 34 (1990)
• [文献書誌] S.Shinkai: "Cation Binding by Macrocycles" Marcel Dekker, 31 (1990)
• [文献書誌] S.Shinkai: "Inclusion Phenomena and Molecular Recognition" Plenum Publishing Co., 8 (1990)
• [文献書誌] F.Toda: "Future Opportunities in Catalytic and Separation Technology" Elsevier, 381 (1990)