1990 Fiscal Year Annual Research Report

包接体結晶を利用した反応系の設計

Research Project

Project/Area Number	02210104
Research Institution	Ehime University
Principal Investigator	戸田芙三夫愛媛大学, 工学部, 教授 (50036232)
Co-Investigator(Kenkyū-buntansha)	小林啓二東京大学, 教養学部, 教授 (50012456) 宮田幹二岐阜大学, 工学部, 助教授 (90029322) 境野芳子群馬大学, 教育学部, 教授 (70008142) 樋口泰一大阪市立大学, 理学部, 教授 (40046868) 藤原隆二島根大学, 理学部, 教授 (10028847)
Keywords	包接 / 固相反応 / 反応制御 / 不斉選択的反応 / 分子設計 / 反応場の設計 / X線結晶構造解析 / 光学分割
Research Abstract	先ず、分子認識能特に不斉認識能に優れたホスト化合物として、酒石酸及びマンデル酸から誘導した光学活性ホストを合成した。数種類のトリフェニルカルビノ-ル基を含むホスト化合物及びアゾ基を含むホスト化合物も合成した。更に興味深いことに、これまでコ-ル酸誘導体しか包接能が無いと信じられていたステロイド系ホストに加えて、コレスタノ-ルやコレステロ-ルも優れた包接能を持つことが判明した(戸田、境野、宮田)。上記の新しいホスト化合物を用いる異性体の分離及び光学分割を行って、これまで分離や分割が能率良く行えなかった物質にも適用できることを見出した。例えば、酒石酸から誘導したホストはアルコ-ル類、シアノヒドリン類及びアセチレンアルコ-ル類に分割の威力を発揮することが判明したし、オキシム類の分割にも始めて成功した。分割で最も興味深い研究成果は、固相でも分割が起こることを見出したことである。例えば、光学活性ホストとラセミ体のβーヨノンオキシドを固相で混合すると、不斉選択的包接が起こり光学活性体が得られた(戸田、小林)。これらのホスト化合物の中には、光学純度決定のためのキラルシフト試剤として有用なものがあることも判明した(戸田)。上記ホストに包接させたゲストを固相で反応させて、不斉選択的合成法を確立する試みも成功した。例えば、酒石酸から誘導したホストに4ーメチル及び3,5ージメチルシクロヘキサノンを包接させた包接錯体を固相でWittig試剤と接触、反応させると光学活性なオレフィンが容易に得られた。その他固相でのアルド-ル縮合やアルコ-ルの置換反応も不斉選択的に進行することを見出した(戸田、境野、宮田、小林)。これらの反応はX線結晶構造解析法によって詳細に研究され、その反応制御の謎を解明すると同時に新しい反応制御の反応系の設計に役立てられ、又強力な回転対陰極型の装置を用いて精度を上げた(藤原、樋口)。

Research Products

(22 results)

All Other

All Publications (22 results)

[Publications] Fumio Toda: "Enantioselective WittigーHorner Reaction in the Solid State" J.Org.Chem.55. 3446-3447 (1990)
[Publications] Fumio Toda: "Isolation of Conformational Isomers of αー and βーIonones by Inclusion Complex Formation" Angew.Chem.Int.Ed.Engl.29. 662-664 (1990)
[Publications] Fumio Toda: "Isolation of Optically Active Oximes" J.Org.Chem.55. 4973-4974 (1990)
[Publications] Fumio Toda: "Efficient Solidーstate Reactions of Alcohols: Dehydration,Rearrangement,and Substitution" J.Chem.Soc.,Chem.Commun. 1270-1271 (1990)
[Publications] Fumio Toda: "Aldol Condensations in the Absence of Solvent: Acceleration of the Reaction and Enhancement of the Stereochemistry" J.Chem.Soc.,Perkin Trans.1. 3207-3209 (1990)
[Publications] Fumio Toda: "Solid State Kinetic Resolution of βーIonone Epoxide and Dialkyl Sulphoxides in the presence of Optically Active Host Compounds" J.Chem.Soc.,Perkin Trans.1. 1591-1593 (1990)
[Publications] Takaji Fujiwara: "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 inTheir Inclusion Complexes with Host." J.Org.Chem.55. 4532-4537 (1990)
[Publications] Takaji Fujiwara: "Structure of αーCyclodextrin 13ー75H_2O" Chem.Lett.739-742 (1990)
[Publications] Takaji Fujiwara: "Crystal and Molecular Structure of the Crystalーline HostーGuest Complex Between (R)ー(+)ー2,2'ーDiーhydroxyー1,1'ーbinaphthyl" Bull.CHem.Soc.Jpn.63. 249-251 (1990)
[Publications] Taiichi Higuchi: "XーRay Structure of the βーCyclodextrinーFerrocene (2:1) Inclusion Compound" J.Chem.Soc.,Perkin Trans 1.1230-1231 (1990)
[Publications] Taiichi Higuchi: "ThreeーDimensional Structure of Aspartate Aminoーtransferase from Escherichia coil and Its Mutant Enzyme at 2.5 A^^ﾟ Resolution" J.Biochem.108. 175-184 (1990)
[Publications] Yoshiko Sakaino: "Inclusion Complexes of a New Host,4,5ーBis(4ーmethoxyphenyl)ー2ー(4ーnitrophenyl)ー1Hーimidazole,with Guests" J.Chem.Soc.,Perkin Trans.1.2852-2854 (1990)
[Publications] Yoshiko Sakaino: "Benzylic Acid Rearrangement in the Solid State" Chem.Lett.373-376 (1990)
[Publications] Yoshiko Sakaino: "Complex Formation of Imidazole Derivatives and Properties of the Products" Mol.Cryst.Liq.Cryst.187. 145-153 (1990)
[Publications] Kanzi Miyata: "Guestーresponsive structural changes in cholic acid intercaration crystals" Nature. 343. 446-447 (1990)
[Publications] Kanzi Miyata: "Polymerization of Diene and Diyne Monomers in Deoxycholic and Apocholic Acid Inclusion Compound" Mol.Cryst.Liq.Cryst.186. 189-195 (1990)
[Publications] Kanzi Miyata: "Inclusion Polymerization of 1ーChlorobutadiene in a Deoxycholic Acid Canal" J.Poly.Sci.,Poly.Chem.28. 1527-1538 (1990)
[Publications] Keiji Kobayasi: "Structure of the Organic Superconductor (DMET)_2ーAuCl_2" Acta Cryst.C46. 1652-1655 (1990)
[Publications] Keiji Kobayasi: "Crystal Structure pf the Organic Metal (DMET)_2BF_4" Bull.Chem.Soc.Jpn.64. 212-215 (1991)
[Publications] Keiji Kobayashi: "Tetrnerized Structure of (DMET)_2ReO_4 and Its Apparent Metallic Behavior in Resistivity" Bull.Chem.Soc.Jpn.63. 1865-1870 (1990)
[Publications] Keiji Kobayasi: "Organic Superconductors,(DMET)_2X" Mol.Crys.Liq.Cryst.185-195 (1990)
[Publications] Fumio Toda: "Future Opprtunities in Catalytic and Separation Technology" Elsevier, 379 (1990)

1990 Fiscal Year Annual Research Report

包接体結晶を利用した反応系の設計

Principal Investigator

戸田 芙三夫 愛媛大学, 工学部, 教授 (50036232)

Research Products

[Publications] Fumio Toda: "Enantioselective WittigーHorner Reaction in the Solid State" J.Org.Chem.55. 3446-3447 (1990)

[Publications] Fumio Toda: "Isolation of Conformational Isomers of αー and βーIonones by Inclusion Complex Formation" Angew.Chem.Int.Ed.Engl.29. 662-664 (1990)

[Publications] Fumio Toda: "Isolation of Optically Active Oximes" J.Org.Chem.55. 4973-4974 (1990)

[Publications] Fumio Toda: "Efficient Solidーstate Reactions of Alcohols: Dehydration,Rearrangement,and Substitution" J.Chem.Soc.,Chem.Commun. 1270-1271 (1990)

[Publications] Fumio Toda: "Aldol Condensations in the Absence of Solvent: Acceleration of the Reaction and Enhancement of the Stereochemistry" J.Chem.Soc.,Perkin Trans.1. 3207-3209 (1990)

[Publications] Fumio Toda: "Solid State Kinetic Resolution of βーIonone Epoxide and Dialkyl Sulphoxides in the presence of Optically Active Host Compounds" J.Chem.Soc.,Perkin Trans.1. 1591-1593 (1990)

[Publications] Takaji Fujiwara: "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 inTheir Inclusion Complexes with Host." J.Org.Chem.55. 4532-4537 (1990)

[Publications] Takaji Fujiwara: "Structure of αーCyclodextrin 13ー75H_2O" Chem.Lett.739-742 (1990)

[Publications] Takaji Fujiwara: "Crystal and Molecular Structure of the Crystalーline HostーGuest Complex Between (R)ー(+)ー2,2'ーDiーhydroxyー1,1'ーbinaphthyl" Bull.CHem.Soc.Jpn.63. 249-251 (1990)

[Publications] Taiichi Higuchi: "XーRay Structure of the βーCyclodextrinーFerrocene (2:1) Inclusion Compound" J.Chem.Soc.,Perkin Trans 1.1230-1231 (1990)

[Publications] Taiichi Higuchi: "ThreeーDimensional Structure of Aspartate Aminoーtransferase from Escherichia coil and Its Mutant Enzyme at 2.5 A^^ﾟ Resolution" J.Biochem.108. 175-184 (1990)

[Publications] Yoshiko Sakaino: "Inclusion Complexes of a New Host,4,5ーBis(4ーmethoxyphenyl)ー2ー(4ーnitrophenyl)ー1Hーimidazole,with Guests" J.Chem.Soc.,Perkin Trans.1.2852-2854 (1990)

[Publications] Yoshiko Sakaino: "Benzylic Acid Rearrangement in the Solid State" Chem.Lett.373-376 (1990)

[Publications] Yoshiko Sakaino: "Complex Formation of Imidazole Derivatives and Properties of the Products" Mol.Cryst.Liq.Cryst.187. 145-153 (1990)

[Publications] Kanzi Miyata: "Guestーresponsive structural changes in cholic acid intercaration crystals" Nature. 343. 446-447 (1990)

[Publications] Kanzi Miyata: "Polymerization of Diene and Diyne Monomers in Deoxycholic and Apocholic Acid Inclusion Compound" Mol.Cryst.Liq.Cryst.186. 189-195 (1990)

[Publications] Kanzi Miyata: "Inclusion Polymerization of 1ーChlorobutadiene in a Deoxycholic Acid Canal" J.Poly.Sci.,Poly.Chem.28. 1527-1538 (1990)

[Publications] Keiji Kobayasi: "Structure of the Organic Superconductor (DMET)_2ーAuCl_2" Acta Cryst.C46. 1652-1655 (1990)

[Publications] Keiji Kobayasi: "Crystal Structure pf the Organic Metal (DMET)_2BF_4" Bull.Chem.Soc.Jpn.64. 212-215 (1991)

[Publications] Keiji Kobayashi: "Tetrnerized Structure of (DMET)_2ReO_4 and Its Apparent Metallic Behavior in Resistivity" Bull.Chem.Soc.Jpn.63. 1865-1870 (1990)

[Publications] Keiji Kobayasi: "Organic Superconductors,(DMET)_2X" Mol.Crys.Liq.Cryst.185-195 (1990)

[Publications] Fumio Toda: "Future Opprtunities in Catalytic and Separation Technology" Elsevier, 379 (1990)

戸田芙三夫愛媛大学, 工学部, 教授 (50036232)