1993 Fiscal Year Annual Research Report

活性異常分子-合成と反応制御

Research Project

Project/Area Number	05303003
Research Institution	University of Tsukuba
Principal Investigator	安藤亘筑波大学, 化学系, 教授 (30008429)
Co-Investigator(Kenkyū-buntansha)	宮仕勉東北大学, 理学部, 教授 (20004442) 富岡秀雄三重大学, 工学部, 教授 (20024599) 鈴木仁美京都大学, 理学部, 教授 (50025342) 小田雅司大阪大学, 理学部, 教授 (60004438) 石川満夫広島大学, 工学部, 教授 (20025985)
Keywords	歪み化合物 / 活性中間体 / ヘテロ原子 / 機能性有機材料 / 反応制御
Research Abstract	本研究は歪み、電荷、原子価、π-共役等により異常な性質を発現する活性分子の合成と反応について理解することを目的とする。本年度は研究分担者を次の3つのグループに分け、それぞれのグループ内で緊密な連係の基に研究を進めた。夏に開催した全体会議の場を活用して、各グループ間の情報交換や共同研究の打ち合わせを行なった。特に基礎研究と応用研究の成果をお互いによく情報交換し効率の良い研究を推進した。(1)新しい異常原子価反応活性種の創出と新規反応性の開拓(井畑、伊輿田、奥、杉森、富岡、長尾、村橋、吉良、宮下)(2)高歪み化合物の合成とその化学的挙動(安藤、西田、松本、永瀬、赤阪、高橋)(3)異常な電荷やπ-共役系を有する分子の合成と機能性材料合成の応用(石川、小倉、小田、沢木、鈴木、宮仕)。活性異常分子の合成法の一つとしてカルベン、シリレン、ゲルミレン等の原子価欠損型活性種を発生させて用いた。さらに、高歪化合物を速度論的に安定化させ単離することを試み、その化学的挙動の検討により結合そのものに関する新しい情報を得た。また、ラジカルイオン種等異常な電荷を有する新規活性種合成やヘテロ原子の特性を利用した新しいπ-共役系の構築を行い機能性有機材料合成への応用を目指した新規反応の開発研究に着手した。本研究対象となる活性異常分子は有機化学の理論、構造、反応の各分野にまたがって広く興味と感心を集めている化合物であり、各分野の第一線の研究者を集めた本研究によって得られる成果は世界に大きなインパクトを与えることが期待され、実際、着実に実績を上げつつある。

Research Products

(33 results)

All Other

All Publications (33 results)

[Publications] Toshiyuki Ohtaki,Yoshio Kabe,Wataru Ando: "Synthesis,Structure and Photoreaction of Bis(germanimines)" Organometallics. 13. 434-435 (1994)
[Publications] T.Kusukawa,Y.Kabe,W.Ando: "Transition Metal Catalyzed Reaction of Peralkylated 3,4-(alkylidene)-1,2-disilacyclobutane" Chemistry Letters. 985-988 (1993)
[Publications] H.Fujihara: "Three-center Selenium Interaction in Electrochemical Oxidation of a Linear Trisselenide" Chemistry Letters. 619-622 (1994)
[Publications] J.Ohshita,H.Hasebe,Y.Masaoka,M.Ishikawa: "Silicon-Carbon Unsaturated Compounds 49.Nickel-Catalyzed Reactions of Adamantyl-2-(trimethylsiloxy)-1,1-bis(trimethyl)Silene" Organometallics. (in press). (1994)
[Publications] Hirofumi Nakano: "The Rhodium(II)Acetate-Catalyzed Reaction of Diacyldiazomethanes with Isothiocvanates:Formation of 2-Thioxo-2H-1,3-oxazin-4(3H)-one" Bull.Chem.Soc.Jpn.66. 238-244 (1993)
[Publications] Toshikazu Ibata: "Formation and Reaction of Azomethine Ylide by the Reaction of Cu(acac)_2-Ketocarbenoids with 1,1-Diphenylmethanimine" Chemistry Letters. 81-84 (1994)
[Publications] Masato Yoshida: "Reaction of C_<60> with Diacyl Peroxides Containing Perfluoroalkyl Groups.The First Example of Electron Transfer Reaction via C_<60>" Tetrahedron Letters. 34. 7629-7632 (1993)
[Publications] Masahiko Iyoda: "Synthesis of the Tris(9-fluorenylidene)cyclopropane Dianion and Related Dianions:[3]Radialenes with Novel Electronic Properties" Angew.Chem,Int.Ed.Engl.32. 89-90 (1993)
[Publications] Masahiko Iyoda: "Synthesis of (1,5-Diazabicyclo[4.3.0]nonan-2-ylidene)pentacarbonylchromium and -tungsten Using Reaction of Carbene Complex" Chemstry Letters. (in press). (1994)
[Publications] A.Oku et al: "Reaction of Carbenes with Cyclic ethers in the Presence of Nucleophiles.A Three-Component Coupling Reaction" Acta Chemica Scandinavica. 47. 391-397 (1993)
[Publications] T.Katsuhira: "Reaction of Propargylic Substrates with triorganozincates.A Novel Method for the Preparation of Allenic Zinc Reagents" Journal of Organic Chemistry. 58. 6166-6168 (1993)
[Publications] Takahiro Fukumoto: "Syntheses of β-Amidovinyltellurides and Oxazoles by Addition Reactions of Alkynes with Benzenetellurinyl Trifluoromethanesulfonate in Acetonitrile" Heteroatom Chemistry. 4. 511-516 (1993)
[Publications] Masaki Irie: "Sythesis of Optically Active Tellurium-Containing Binaphthyls and Their Use in the Asymmetric 1,4-Addition of α,β-Unsaturated Kitones" Tetrahedron Asymmetry. 4. 2127-2130 (1993)
[Publications] Masaji Oda: "Regioselective Lethiations of Di(2-thienyl)methane:A Celean Kinetic and Thermodynamic Controlin Lithiation" Tetrahedron Letters. 4. 8143-8146 (1993)
[Publications] S.Tsuji: "Phosphadioxirane Intermediates in the Reaction of Singlet Oxygen with Phosphites and Phosphines" J.Org.Chem.58. 5055-5059 (1993)
[Publications] K.Takagi: "Controlled Photocycloaddition of Unsaturated Carboxylates Intercalated In Hydrotalcite Clay Interlayers" J.Am.Chem.Soc.115. 4339-4344 (1993)
[Publications] Akira Sugimori: "Formation and Photochemical and Thermal Reactions of Adduct between 1,2,5,3-Cobaltadithiazole and Dimethyl Acethlendicarboxlate" Chem.Lett.1994. 473-476 (1994)
[Publications] Akira Sugimori: "Photochemical Reactions of Several Adducts of Metalladithiolenes and Metalladithiazones-Dissociation and Rearrangement" Coord.Chem.Rev.(in press).
[Publications] Akira Sugimori: "A Novel Metallacycle,1,2,5,3-Cobaltadithiazole.Formation,Structure and Properties of (Cp)(phenylmethanimine-N.1-dithiolato)cobalt(III)" J.Organomet.Chem.(in press).
[Publications] Hitomi Suzuki: "Synthesis and First X-ray Analysis of a atabilized Chiral Chlorobismuthine Fixation of Molecular Geometry Induced by the Intramolecular Coordination of a Sulfonyl Group" J.Chem.Soc.,Perkin Trans.1. 1169-1175 (1993)
[Publications] Hitomi Suzuki: "Chiral Chlorobismuthines Stabilized by the Intramolecular Coordination of an N,N-Dimethylamino Group.X-ray Structure Analysis,Asymmetric Induction at Bismuth Center,Dynamic Behaviour in Solution" J.Chem.Soc.,Perkin Trans.1. 2969-2973 (1993)
[Publications] Y.Nagao: "New Intramolecular Five-Endo-Mode Cyclization of Allenyl Aryl Ketones" Chemistry Letters. 389-392 (1994)
[Publications] Y.Nagao: "New six-to Eight-Membered-Ring Formation Based on the Intramolecular Endo Mode Ring Closure of Allenyl(Substituted Phenyl)alkyl Ketones" Chemistry Letters. 597-600 (1994)
[Publications] S.Nagase: "Metallotullerenes MC_<82>(M=Sc,Y,and La).A Theoretical Study of the Electronic and Structural Aspects" Chem.Phys.Lett.214. 57-63 (1993)
[Publications] S.Kyushin: "Selective Si-Si Bond Cleavage in Decaisopropylbicyclo[2,2,0]hexasilane.A Route to Sterically Hindered 1,4-dichlorocyclohexasilanes" Chemistry Letters. 221-224 (1994)
[Publications] H.Ikeda: "Substitution Effects on Regioselective Cyclizations of 1,5-and 2,4-Diphenyl-1,5-hexadiene Cation Radicals" Tetrahedron Lett.34. 2323-2326 (1993)
[Publications] H.Ikeda: "The Cation Radical Cope Rearrangement of 2,5-Diphenyl-1,5-hexadienes under Electron Ionization" J.Chem.Soc.,Chem.Commun.367-369 (1993)
[Publications] Y.Takahashi: "Electron Transfer Photochemisty of Endoperoxides" J.Chem.Soc.,Perkins.2. 243-253 (1993)
[Publications] M.Kira: "Extraordinary Large Red Shift of the n(Si)→3p(Si) Transition of Silylenes Caused by Trimethylsilyl and Trimethylgermyl Substituents" Chem.Lett.1345-1348 (1993)
[Publications] A.Miyashita,M.Hotta,Y.Saida: "Selective Sp^3 C-H Bond Activation of fAlkylaromatics by Platinum Complexes" J.Organomet.Chem.(in press). (1994)
[Publications] N.Tokitoh: "The First Stable Stannaethione in Solution Dirived from a Kinetically Stabilized Diarylstannylene" J.Am.Chem.Soc.115. 2065-2066 (1993)
[Publications] M.Kira: "Trialkyltin Cation in solution" J.Organomet.Chem.(in press), (1993)
[Publications] 宮下晃: "季刊化学総説「前周期遷移金属の有機化学」 (分担)" 学会出版センター, 207 (1993)

1993 Fiscal Year Annual Research Report

活性異常分子-合成と反応制御

Principal Investigator

安藤 亘 筑波大学, 化学系, 教授 (30008429)

Research Products

[Publications] Toshiyuki Ohtaki,Yoshio Kabe,Wataru Ando: "Synthesis,Structure and Photoreaction of Bis(germanimines)" Organometallics. 13. 434-435 (1994)

[Publications] T.Kusukawa,Y.Kabe,W.Ando: "Transition Metal Catalyzed Reaction of Peralkylated 3,4-(alkylidene)-1,2-disilacyclobutane" Chemistry Letters. 985-988 (1993)

[Publications] H.Fujihara: "Three-center Selenium Interaction in Electrochemical Oxidation of a Linear Trisselenide" Chemistry Letters. 619-622 (1994)

[Publications] J.Ohshita,H.Hasebe,Y.Masaoka,M.Ishikawa: "Silicon-Carbon Unsaturated Compounds 49.Nickel-Catalyzed Reactions of Adamantyl-2-(trimethylsiloxy)-1,1-bis(trimethyl)Silene" Organometallics. (in press). (1994)

[Publications] Hirofumi Nakano: "The Rhodium(II)Acetate-Catalyzed Reaction of Diacyldiazomethanes with Isothiocvanates:Formation of 2-Thioxo-2H-1,3-oxazin-4(3H)-one" Bull.Chem.Soc.Jpn.66. 238-244 (1993)

[Publications] Toshikazu Ibata: "Formation and Reaction of Azomethine Ylide by the Reaction of Cu(acac)_2-Ketocarbenoids with 1,1-Diphenylmethanimine" Chemistry Letters. 81-84 (1994)

[Publications] Masato Yoshida: "Reaction of C_<60> with Diacyl Peroxides Containing Perfluoroalkyl Groups.The First Example of Electron Transfer Reaction via C_<60>" Tetrahedron Letters. 34. 7629-7632 (1993)

[Publications] Masahiko Iyoda: "Synthesis of the Tris(9-fluorenylidene)cyclopropane Dianion and Related Dianions:[3]Radialenes with Novel Electronic Properties" Angew.Chem,Int.Ed.Engl.32. 89-90 (1993)

[Publications] Masahiko Iyoda: "Synthesis of (1,5-Diazabicyclo[4.3.0]nonan-2-ylidene)pentacarbonylchromium and -tungsten Using Reaction of Carbene Complex" Chemstry Letters. (in press). (1994)

[Publications] A.Oku et al: "Reaction of Carbenes with Cyclic ethers in the Presence of Nucleophiles.A Three-Component Coupling Reaction" Acta Chemica Scandinavica. 47. 391-397 (1993)

[Publications] T.Katsuhira: "Reaction of Propargylic Substrates with triorganozincates.A Novel Method for the Preparation of Allenic Zinc Reagents" Journal of Organic Chemistry. 58. 6166-6168 (1993)

[Publications] Takahiro Fukumoto: "Syntheses of β-Amidovinyltellurides and Oxazoles by Addition Reactions of Alkynes with Benzenetellurinyl Trifluoromethanesulfonate in Acetonitrile" Heteroatom Chemistry. 4. 511-516 (1993)

[Publications] Masaki Irie: "Sythesis of Optically Active Tellurium-Containing Binaphthyls and Their Use in the Asymmetric 1,4-Addition of α,β-Unsaturated Kitones" Tetrahedron Asymmetry. 4. 2127-2130 (1993)

[Publications] Masaji Oda: "Regioselective Lethiations of Di(2-thienyl)methane:A Celean Kinetic and Thermodynamic Controlin Lithiation" Tetrahedron Letters. 4. 8143-8146 (1993)

[Publications] S.Tsuji: "Phosphadioxirane Intermediates in the Reaction of Singlet Oxygen with Phosphites and Phosphines" J.Org.Chem.58. 5055-5059 (1993)

[Publications] K.Takagi: "Controlled Photocycloaddition of Unsaturated Carboxylates Intercalated In Hydrotalcite Clay Interlayers" J.Am.Chem.Soc.115. 4339-4344 (1993)

[Publications] Akira Sugimori: "Formation and Photochemical and Thermal Reactions of Adduct between 1,2,5,3-Cobaltadithiazole and Dimethyl Acethlendicarboxlate" Chem.Lett.1994. 473-476 (1994)

[Publications] Akira Sugimori: "Photochemical Reactions of Several Adducts of Metalladithiolenes and Metalladithiazones-Dissociation and Rearrangement" Coord.Chem.Rev.(in press).

[Publications] Akira Sugimori: "A Novel Metallacycle,1,2,5,3-Cobaltadithiazole.Formation,Structure and Properties of (Cp)(phenylmethanimine-N.1-dithiolato)cobalt(III)" J.Organomet.Chem.(in press).

[Publications] Hitomi Suzuki: "Synthesis and First X-ray Analysis of a atabilized Chiral Chlorobismuthine Fixation of Molecular Geometry Induced by the Intramolecular Coordination of a Sulfonyl Group" J.Chem.Soc.,Perkin Trans.1. 1169-1175 (1993)

[Publications] Hitomi Suzuki: "Chiral Chlorobismuthines Stabilized by the Intramolecular Coordination of an N,N-Dimethylamino Group.X-ray Structure Analysis,Asymmetric Induction at Bismuth Center,Dynamic Behaviour in Solution" J.Chem.Soc.,Perkin Trans.1. 2969-2973 (1993)

[Publications] Y.Nagao: "New Intramolecular Five-Endo-Mode Cyclization of Allenyl Aryl Ketones" Chemistry Letters. 389-392 (1994)

[Publications] Y.Nagao: "New six-to Eight-Membered-Ring Formation Based on the Intramolecular Endo Mode Ring Closure of Allenyl(Substituted Phenyl)alkyl Ketones" Chemistry Letters. 597-600 (1994)

[Publications] S.Nagase: "Metallotullerenes MC_<82>(M=Sc,Y,and La).A Theoretical Study of the Electronic and Structural Aspects" Chem.Phys.Lett.214. 57-63 (1993)

[Publications] S.Kyushin: "Selective Si-Si Bond Cleavage in Decaisopropylbicyclo[2,2,0]hexasilane.A Route to Sterically Hindered 1,4-dichlorocyclohexasilanes" Chemistry Letters. 221-224 (1994)

[Publications] H.Ikeda: "Substitution Effects on Regioselective Cyclizations of 1,5-and 2,4-Diphenyl-1,5-hexadiene Cation Radicals" Tetrahedron Lett.34. 2323-2326 (1993)

[Publications] H.Ikeda: "The Cation Radical Cope Rearrangement of 2,5-Diphenyl-1,5-hexadienes under Electron Ionization" J.Chem.Soc.,Chem.Commun.367-369 (1993)

[Publications] Y.Takahashi: "Electron Transfer Photochemisty of Endoperoxides" J.Chem.Soc.,Perkins.2. 243-253 (1993)

[Publications] M.Kira: "Extraordinary Large Red Shift of the n(Si)→3p(Si) Transition of Silylenes Caused by Trimethylsilyl and Trimethylgermyl Substituents" Chem.Lett.1345-1348 (1993)

[Publications] A.Miyashita,M.Hotta,Y.Saida: "Selective Sp^3 C-H Bond Activation of fAlkylaromatics by Platinum Complexes" J.Organomet.Chem.(in press). (1994)

[Publications] N.Tokitoh: "The First Stable Stannaethione in Solution Dirived from a Kinetically Stabilized Diarylstannylene" J.Am.Chem.Soc.115. 2065-2066 (1993)

[Publications] M.Kira: "Trialkyltin Cation in solution" J.Organomet.Chem.(in press), (1993)

[Publications] 宮下 晃: "季刊 化学総説「前周期遷移金属の有機化学」 (分担)" 学会出版センター, 207 (1993)

安藤亘筑波大学, 化学系, 教授 (30008429)

[Publications] 宮下晃: "季刊化学総説「前周期遷移金属の有機化学」 (分担)" 学会出版センター, 207 (1993)