1989 年度実績報告書

異種原子間電子移動の特性と化学的機能

研究課題

研究課題/領域番号	63303009
研究機関	岡山大学
研究代表者	鳥居滋岡山大学, 工学部, 教授 (70032927)
研究分担者	山本尚名古屋大学, 工学部, 教授 (10135311) 諸岡良彦東京工業大学, 資源化学研究所, 教授 (70016731) 中井武東京工業大学, 工学部, 教授 (90016717) 村井真二大阪大学, 工学部, 教授 (00029050) 内本喜一郎京都大学, 工学部, 教授 (90025958)
キーワード	異種原子間電子移動 / 有機金属錯体 / 複合金属レドックス系 / 有機電解反応 / 光誘起電子移動反応 / 複合金属系触媒反応 / エナンチオ区別反応 / 不斉触媒反応
研究概要	平成元年度は、前年度に引き続き、つぎの4研究課題について、相互に綿密な情報交換を行ないながら、有機的な研究を分担とて行った。 1)有機化合物における異種原子間電子移動の特性と化学的機能 2)触媒活性有機金属化合物における異種原子間電子移動の特性と化学的機能 3)異種原子間電子移動の特性に及ぼす物理学的手法の効果とその合成化学的展開 4)異種原子間電子移動の有機合成への展開まず、新しい異種原子間電子移動反応系の設計と、その化学的機能及び特性に関する研究では、Ti/Zn,Pb/Al,Co/Cr,Ni/Pb/Alの他、今年度は、Ti/Al,Nb/ZnやTa/Zn等にも拡張し、これら二成分系及び三成分系の異種原子間電子移動の特性を、究明することにより、それぞれの複合金属レドックス系に特徴的な、新しい炭素ー炭素結合形成反応を、惹起することに成功した。また、鉄、コバルト、ニッケル、白金、ロジウム、ルテニウム等の触媒活性有機金属化合物と、種々のケイ素化合物、オレフィン、アルキン等の有機化合物とで構成される複合レドックス系に於ける、異種原子間電子移動過程の解明や、その特性を生かした、新しい高選択的反応の開発を行なった。さらに、生体系での物質代謝にかかわる、酵素と酵素の間の電子移動反応の制御と酵素間認識を解明するため、新しいモデル系の合成と、その電子移動経路の検討を行なった。光、電気等の物理学的手法により誘起される、電子移動反応系に関する研究では、キノン/NADH、4B族有機金属/共役オレフィン、ビニルハライド/スルフィド等の酸化還元系に於ける、異種原子間電子伝達機構の解明と、その特性を生かした、新しい電子触媒系の開発に成功している。一方、異種原子間電子移動反応の有機合成への展開として、不斉炭素ー炭素結合形成反応を中心に、多くの研究成果を挙げている。代表的なものを列挙すれば、グリオキシ酸エステルの不斉エン反応によるαーヒドロキシエステルの合成、不斉[2+2]付加環化反応、大環状ジアルキニルイミンの合成、回転異性体制御によるジアステレオ面区別反応、αーアミノ酸のキラル転写、オレフィンのヒドロシリル化、特異的酸素酸化等が挙げられる。以上、研究計画に記載した全課題について、研究は順調に進歩しており、今後、異種原子間電子移動反応の基礎、応用、両面での加速度的な展開が期待できる。

研究成果

(45件)

すべてその他

すべて文献書誌

[文献書誌] Hideo TANAKA: "Peductive Addition of Polyhalomethanes and Their Related Compounds to Aldehydes and 1,2-Elomonation of the Coupling Products in a Pb/Al Bimetal Redox System" J.ORG.CHEM.54. 444-450 (1989)
[文献書誌] Hideo TANAKA: "Reduction Dimerization of Vinyl Hanyl Halides in an Ni/Pb/Al Three Metal Redox System.A Facile Access to Terphenyl Derivatives" TETRAHEDRON LETT.30. 1261-1264 (1989)
[文献書誌] Hideo TANAKA: "Electroreductive"Barbier Type"Allylation of Imines with a Combination of a Pb(O)/Pb(II)Redox Mediator and Sacrificial Anode(Al)" TETRAHEDRON LETT.30. 4161-4164 (1989)
[文献書誌] Hideo TANAKA: "A Facile Electroreductive Hydrocoupling of Imines in an Undivided Cell" SYNLETT. 51-52 (1989)
[文献書誌] Joji OHSHITA: "Platium-Catalyzed Reactions of Phenylethyldisilanes" CHEM.EXPRESS,. 3. 179-182 (1988)
[文献書誌] Mitsuo ISHIKAWA: "Silicon-carbon Unsaturated Compounds XXIII.Transition-metal-catalyzed Formation of Silenes from Vinyldisilanes" J.ORGANOMET.CHEM.363. C1-C3 (1989)
[文献書誌] Joji OHSHITA: "Silicon-Carbon Unsaturated Compounds.24.Some Reactions of a Nickelasilacyclobutene" Organometallics. 8. 2050-2054 (1989)
[文献書誌] Kohei TAMAO: "Nickel(O)-Promoted Cyclization Enynes with Isocyanides:A New Route to Polycyclic Cyclopenone Skeletones" J.AM.CHEM.SOC.110. 1286-1288 (1988)
[文献書誌] Yoshihiko ITO: "Palladium-catalyzed Coupling of N-Substituted Isocyanide Dichlorides with Alkynyltin Compounds:New Synthesis of Dialykynylketones" Tetrahedron Lett.29. 5379-5382 (1989)
[文献書誌] Kohei TAMAO: "Nickel(O)-Promoted Cyclization of 1,n-Diynes with Isocyanide:The First Practical Synthesis of Polycyclic Iminocyclopentadienes" J.Org.Chem.54. 3517-3519 (1989)
[文献書誌] Yoshihiko ITO: "Synthesis of Unsymmetrical Dialkynyl Imines.Stepwise Coupling of N-Phenyl Phenylthioimidoyl Chloride with Alkynyltin Compounds" Chem.Lett.1261-1264 (1989)
[文献書誌] Kazuhiko TAKAI: "Preparation of Alkylchromiun Reagents by Reduction of Alkyl Halides with Chromium(II)Chloride under Cabalt Catalysis" J.Org.Chem.54. 4732-4734 (1989)
[文献書誌] Kazuhiko TAKAI: "Preparation of β-Hetero-Substituted Alkenylsilanes from Carboxylic Acid Derivatives" Synlett. 27-28 (1989)
[文献書誌] Kazuhiko TAKAI: "Preparation of Alkenyl Sulfides and Enamines by Alkylidenation of Carboxylic Acid Derivatives" Tetrahedron Lett.30. 211-214 (1989)
[文献書誌] Kazuhiko TAKAI: "Stereoselective Addition of α-Chloro Allylic Chromium Reagents to Aldehydes" Tetrahedron Lett.30. 4389-4392 (1989)
[文献書誌] Yasutaka KATAOKA: "Reduction of Acetylenes to(Z)-Olefins by Means of Low-Valent Niobium or Tantalum" Tetrahedron Lett.31. 365-368 (1990)
[文献書誌] Yasutaka KATAOKA: "Preparation of 1-Naphthols from Acetylenes and o-Phthalaldehyde Using Low-Valent Tantalum and Niobium" Tetrahedron Lett.31. 369-372 (1990)
[文献書誌] Kenji UNEYAMA: "Generation and Reaction of 2,2,2-Trifluoro-1-Phenylsulfenylethyl Carbocation" Tetrahedron Lett.30. 2265-2266 (1989)
[文献書誌] Kenji UNEYAMA: "Trifluoroacetimidoyl Chlorides as a New Trifluoromethyl Building Block for Fluorinated Nitrogen Heterocycles" Tetrahedron Lett.30. 4821-4824 (1989)
[文献書誌] Shinobu ITO: "Efficient NAD^+-Regeneration System with Heteroaromatic o-Quinones and Molecular Oxygen" J.Chem.Soc.,Chem.Commun.694-695 (1989)
[文献書誌] Kazuhiko MIZUNO: "Generation of Organic Cations from Group 14 Organometallic Compounds via Photoinduced Electron Transfer in the Presence of Cu(II)Salt" Chem.Lett.229-232 (1988)
[文献書誌] Kazuhiko MIZUNO: "Dual Regioselectivity in the Photoallylation of Electron-Deficient Alkenes by Allylic Silanes" Chem.Lett.1507-1510 (1988)
[文献書誌] Kazuhiko MIZUNO: "Photosubstitution of Dicyanobenzenes by Group 14 Organometallic Compounds via Photoinduced Electron-Transfer.Addtive and Medium Effects on Photoinduced Electron Transfer Reaction" Chem.Lett.1833-1836 (1988)
[文献書誌] Kazuhiko MIZUNO: "Photosilylation of Electron-Deficient Alkenes by Use of Disilanes via Photoinduced Electron-Transfer" Tetrahedron Lett.30. 3689-3692 (1989)
[文献書誌] Akihiro SUZUKI: "Preparation and Properties of Reconstituted Myoglobins of with Chemically Modified Hemes." Journal of the Chemical SOciety of Japan. 505-511 (1988)
[文献書誌] Masao TOKUDA: "An Efficient Electrochemical Coupling of Allylic Halides by Using a Copper Anode" Chem.Lett.945-948 (1988)
[文献書誌] Masao TOKUDA: "Regioselectivity in Electrochemical Allylation of Carbonyl Compounds.A Synthesis of Egomaketone by Regioselective Allylation" J.Org.Chem.54. 5608-5613 (1989)
[文献書誌] Tsugio KITAMURA: "Photolysis of β-(o-Methylthiophehyl)vinyl Bromides.A Versatile Synthesis of Benzo[b]thiophenes" Chem.Lett.1637-1638 (1988)
[文献書誌] Koichi MIKAMI: "Various Chiral Dialkoxy Titanium Complexes as an Asymmetric Catalyst for Glyoxylate-ene Reaction" Chem.Express. 4. 589-593 (1989)
[文献書誌] Koichi MIKAMI: "Asymmetric Glyoxylate-Ene Reaction Catalyzed by Chiral Titanium Complexes:A Practical Access to α-Hydroxy Esters in High Enantiomeric Purities" J.Am.Chem.Soc.111. 1940-1941 (1989)
[文献書誌] Yujiro HAYASHI: "Asymmetric[2+2]Cycloaddition Reaction Catalyzed by a Chiral Titanium Reagent" Chem.Lett.793-796 (1989)
[文献書誌] Hideo KUROSAWA: "An Unusually Lower Barrier to Reductive Elimination of an 18-Electron η^3-Allyl(organo)nickerl(II)Complex Than Those of a 16-Electron η^3-Allyl Counterpart and a 16-Electron η^1-Allyl Isomer" J.Am.Chem.Soc.110. 6272-6273 (1988)
[文献書誌] Toshiaki MURAI: "Cobalt Carbonyl Catalyzed Reactions of Cyclic Ethers with a Hydrosilane and Carbon Monoxide.A New Synthetic Reaction Equivalent to Nucleophilic Oxymethylation" J.Am.Chem.Soc.111. 7938-7946 (1989)
[文献書誌] Takahiro HOSOKAWA: "Pd(II)-Catalyzed Reactions of Olefins with Oxygen Nucleophiles" Journal of Synthetic Organic Chemostry,Japan. 47. 636-648 (1989)
[文献書誌] Seiki SAITO: "Rotamer Distribution Control and Double Michael Addition for Cyclopentane Annulation with Superb Selectivity" J.Am.Chem.Soc.111. 4533-4535 (1989)
[文献書誌] Munetaka AKITA: "Metal-exchange Reaction on Cationic Diiron μ-η^2-(C,O)-enolate Complexes" J.Organomet.Chem.345. C9-C12 (1988)
[文献書誌] Munetaka AKITA: "One-pot Synthesis of Transition Metal-Substituted Carbowylic Acid" J.Organomet.Chem.348. 91-94 (1988)
[文献書誌] Munetaka AKITA: "Preparation of Homo-and Heterobimetallic μ-η^2-(C,C)-Ketene Complexes,FpCH_2COMLn,and Transformation of the Bridging Ketene Ligand into Various C2 Functional Groups" Organometallics. 7. 366-374 (1988)
[文献書誌] Munetaka AKITA: "Modelling the Pichler-Schulz Mechanism by Catalytic Hydrosilylation of Acyl Metal Complexes" J.Chem.Soc.,Chem.Commun.527-529 (1989)
[文献書誌] Munetaka AKITA: "Molecular Structure of Heterobimetallic μ-η^2-(C,C)-Ketene Complexes" J.Chem.Soc.Dalton Trans.1627-1630 (1989)
[文献書誌] Munetaka AKITA: "Metal-Exchange Reaction on Cationic Polyiron μ_3-η^30(C,C,O)-Ketene and μ-η^2-(C,O)-Enolate Complexes" Organometallics. 8. 687-693 (1989)
[文献書誌] Munetaka AKITA: "Reactivities of Ketene Ligands on Polymetallic Systems" J.Mol.Catal.56. 107 (1989)
[文献書誌] Akira Yanagusawa: "Double Alkylation of α,β-Unsaturated Acetals.An Inverse Polarity Approach" J.Am.Chem.Soc.111. 366-368 (1989)
[文献書誌] Sigeru TORII: "Topics in Current Chemistry,Vol.148" Springer-Verlag,Barlin-Heidelberg, 41 (1988)
[文献書誌] Sigeru TOTII: "Organic Electrochemistry,3rd Edition" Marcel Dekker,inc.,New York, (1989)

1989 年度 実績報告書

異種原子間電子移動の特性と化学的機能

研究代表者

鳥居 滋 岡山大学, 工学部, 教授 (70032927)

研究成果

[文献書誌] Hideo TANAKA: "Peductive Addition of Polyhalomethanes and Their Related Compounds to Aldehydes and 1,2-Elomonation of the Coupling Products in a Pb/Al Bimetal Redox System" J.ORG.CHEM.54. 444-450 (1989)

[文献書誌] Hideo TANAKA: "Reduction Dimerization of Vinyl Hanyl Halides in an Ni/Pb/Al Three Metal Redox System.A Facile Access to Terphenyl Derivatives" TETRAHEDRON LETT.30. 1261-1264 (1989)

[文献書誌] Hideo TANAKA: "Electroreductive"Barbier Type"Allylation of Imines with a Combination of a Pb(O)/Pb(II)Redox Mediator and Sacrificial Anode(Al)" TETRAHEDRON LETT.30. 4161-4164 (1989)

[文献書誌] Hideo TANAKA: "A Facile Electroreductive Hydrocoupling of Imines in an Undivided Cell" SYNLETT. 51-52 (1989)

[文献書誌] Joji OHSHITA: "Platium-Catalyzed Reactions of Phenylethyldisilanes" CHEM.EXPRESS,. 3. 179-182 (1988)

[文献書誌] Mitsuo ISHIKAWA: "Silicon-carbon Unsaturated Compounds XXIII.Transition-metal-catalyzed Formation of Silenes from Vinyldisilanes" J.ORGANOMET.CHEM.363. C1-C3 (1989)

[文献書誌] Joji OHSHITA: "Silicon-Carbon Unsaturated Compounds.24.Some Reactions of a Nickelasilacyclobutene" Organometallics. 8. 2050-2054 (1989)

[文献書誌] Kohei TAMAO: "Nickel(O)-Promoted Cyclization Enynes with Isocyanides:A New Route to Polycyclic Cyclopenone Skeletones" J.AM.CHEM.SOC.110. 1286-1288 (1988)

[文献書誌] Yoshihiko ITO: "Palladium-catalyzed Coupling of N-Substituted Isocyanide Dichlorides with Alkynyltin Compounds:New Synthesis of Dialykynylketones" Tetrahedron Lett.29. 5379-5382 (1989)

[文献書誌] Kohei TAMAO: "Nickel(O)-Promoted Cyclization of 1,n-Diynes with Isocyanide:The First Practical Synthesis of Polycyclic Iminocyclopentadienes" J.Org.Chem.54. 3517-3519 (1989)

[文献書誌] Yoshihiko ITO: "Synthesis of Unsymmetrical Dialkynyl Imines.Stepwise Coupling of N-Phenyl Phenylthioimidoyl Chloride with Alkynyltin Compounds" Chem.Lett.1261-1264 (1989)

[文献書誌] Kazuhiko TAKAI: "Preparation of Alkylchromiun Reagents by Reduction of Alkyl Halides with Chromium(II)Chloride under Cabalt Catalysis" J.Org.Chem.54. 4732-4734 (1989)

[文献書誌] Kazuhiko TAKAI: "Preparation of β-Hetero-Substituted Alkenylsilanes from Carboxylic Acid Derivatives" Synlett. 27-28 (1989)

[文献書誌] Kazuhiko TAKAI: "Preparation of Alkenyl Sulfides and Enamines by Alkylidenation of Carboxylic Acid Derivatives" Tetrahedron Lett.30. 211-214 (1989)

[文献書誌] Kazuhiko TAKAI: "Stereoselective Addition of α-Chloro Allylic Chromium Reagents to Aldehydes" Tetrahedron Lett.30. 4389-4392 (1989)

[文献書誌] Yasutaka KATAOKA: "Reduction of Acetylenes to(Z)-Olefins by Means of Low-Valent Niobium or Tantalum" Tetrahedron Lett.31. 365-368 (1990)

[文献書誌] Yasutaka KATAOKA: "Preparation of 1-Naphthols from Acetylenes and o-Phthalaldehyde Using Low-Valent Tantalum and Niobium" Tetrahedron Lett.31. 369-372 (1990)

[文献書誌] Kenji UNEYAMA: "Generation and Reaction of 2,2,2-Trifluoro-1-Phenylsulfenylethyl Carbocation" Tetrahedron Lett.30. 2265-2266 (1989)

[文献書誌] Kenji UNEYAMA: "Trifluoroacetimidoyl Chlorides as a New Trifluoromethyl Building Block for Fluorinated Nitrogen Heterocycles" Tetrahedron Lett.30. 4821-4824 (1989)

[文献書誌] Shinobu ITO: "Efficient NAD^+-Regeneration System with Heteroaromatic o-Quinones and Molecular Oxygen" J.Chem.Soc.,Chem.Commun.694-695 (1989)

[文献書誌] Kazuhiko MIZUNO: "Generation of Organic Cations from Group 14 Organometallic Compounds via Photoinduced Electron Transfer in the Presence of Cu(II)Salt" Chem.Lett.229-232 (1988)

[文献書誌] Kazuhiko MIZUNO: "Dual Regioselectivity in the Photoallylation of Electron-Deficient Alkenes by Allylic Silanes" Chem.Lett.1507-1510 (1988)

[文献書誌] Kazuhiko MIZUNO: "Photosubstitution of Dicyanobenzenes by Group 14 Organometallic Compounds via Photoinduced Electron-Transfer.Addtive and Medium Effects on Photoinduced Electron Transfer Reaction" Chem.Lett.1833-1836 (1988)

[文献書誌] Kazuhiko MIZUNO: "Photosilylation of Electron-Deficient Alkenes by Use of Disilanes via Photoinduced Electron-Transfer" Tetrahedron Lett.30. 3689-3692 (1989)

[文献書誌] Akihiro SUZUKI: "Preparation and Properties of Reconstituted Myoglobins of with Chemically Modified Hemes." Journal of the Chemical SOciety of Japan. 505-511 (1988)

[文献書誌] Masao TOKUDA: "An Efficient Electrochemical Coupling of Allylic Halides by Using a Copper Anode" Chem.Lett.945-948 (1988)

[文献書誌] Masao TOKUDA: "Regioselectivity in Electrochemical Allylation of Carbonyl Compounds.A Synthesis of Egomaketone by Regioselective Allylation" J.Org.Chem.54. 5608-5613 (1989)

[文献書誌] Tsugio KITAMURA: "Photolysis of β-(o-Methylthiophehyl)vinyl Bromides.A Versatile Synthesis of Benzo[b]thiophenes" Chem.Lett.1637-1638 (1988)

[文献書誌] Koichi MIKAMI: "Various Chiral Dialkoxy Titanium Complexes as an Asymmetric Catalyst for Glyoxylate-ene Reaction" Chem.Express. 4. 589-593 (1989)

[文献書誌] Koichi MIKAMI: "Asymmetric Glyoxylate-Ene Reaction Catalyzed by Chiral Titanium Complexes:A Practical Access to α-Hydroxy Esters in High Enantiomeric Purities" J.Am.Chem.Soc.111. 1940-1941 (1989)

[文献書誌] Yujiro HAYASHI: "Asymmetric[2+2]Cycloaddition Reaction Catalyzed by a Chiral Titanium Reagent" Chem.Lett.793-796 (1989)

[文献書誌] Hideo KUROSAWA: "An Unusually Lower Barrier to Reductive Elimination of an 18-Electron η^3-Allyl(organo)nickerl(II)Complex Than Those of a 16-Electron η^3-Allyl Counterpart and a 16-Electron η^1-Allyl Isomer" J.Am.Chem.Soc.110. 6272-6273 (1988)

[文献書誌] Toshiaki MURAI: "Cobalt Carbonyl Catalyzed Reactions of Cyclic Ethers with a Hydrosilane and Carbon Monoxide.A New Synthetic Reaction Equivalent to Nucleophilic Oxymethylation" J.Am.Chem.Soc.111. 7938-7946 (1989)

[文献書誌] Takahiro HOSOKAWA: "Pd(II)-Catalyzed Reactions of Olefins with Oxygen Nucleophiles" Journal of Synthetic Organic Chemostry,Japan. 47. 636-648 (1989)

[文献書誌] Seiki SAITO: "Rotamer Distribution Control and Double Michael Addition for Cyclopentane Annulation with Superb Selectivity" J.Am.Chem.Soc.111. 4533-4535 (1989)

[文献書誌] Munetaka AKITA: "Metal-exchange Reaction on Cationic Diiron μ-η^2-(C,O)-enolate Complexes" J.Organomet.Chem.345. C9-C12 (1988)

[文献書誌] Munetaka AKITA: "One-pot Synthesis of Transition Metal-Substituted Carbowylic Acid" J.Organomet.Chem.348. 91-94 (1988)

[文献書誌] Munetaka AKITA: "Preparation of Homo-and Heterobimetallic μ-η^2-(C,C)-Ketene Complexes,FpCH_2COMLn,and Transformation of the Bridging Ketene Ligand into Various C2 Functional Groups" Organometallics. 7. 366-374 (1988)

[文献書誌] Munetaka AKITA: "Modelling the Pichler-Schulz Mechanism by Catalytic Hydrosilylation of Acyl Metal Complexes" J.Chem.Soc.,Chem.Commun.527-529 (1989)

[文献書誌] Munetaka AKITA: "Molecular Structure of Heterobimetallic μ-η^2-(C,C)-Ketene Complexes" J.Chem.Soc.Dalton Trans.1627-1630 (1989)

[文献書誌] Munetaka AKITA: "Metal-Exchange Reaction on Cationic Polyiron μ_3-η^30(C,C,O)-Ketene and μ-η^2-(C,O)-Enolate Complexes" Organometallics. 8. 687-693 (1989)

[文献書誌] Munetaka AKITA: "Reactivities of Ketene Ligands on Polymetallic Systems" J.Mol.Catal.56. 107 (1989)

[文献書誌] Akira Yanagusawa: "Double Alkylation of α,β-Unsaturated Acetals.An Inverse Polarity Approach" J.Am.Chem.Soc.111. 366-368 (1989)

[文献書誌] Sigeru TORII: "Topics in Current Chemistry,Vol.148" Springer-Verlag,Barlin-Heidelberg, 41 (1988)

[文献書誌] Sigeru TOTII: "Organic Electrochemistry,3rd Edition" Marcel Dekker,inc.,New York, (1989)

1989 年度実績報告書

鳥居滋岡山大学, 工学部, 教授 (70032927)