1992 Fiscal Year Annual Research Report

生体系複合場金属錯体による新反応系の構築

Research Project

Project/Area Number	04225107
Research Institution	Okazaki National Research Institutes
Principal Investigator	田中晃二岡崎国立共同研究機構, 分子科学研究所, 教授 (00029274)
Co-Investigator(Kenkyū-buntansha)	長野哲雄東京大学, 藥学部, 助教授 (20111552) 船引卓三京都大学, 工学部, 助教授 (70026061) 北島信正東京工業大学, 資源化学研究所, 助教授 (20177843) 矢野重信奈良女子大学, 理学部, 教授 (60011186)
Keywords	二酸化炭素固定 / α-ケト酸 / オキシヘモシアニン / オキシチロシナーゼ / オキシゲナーゼ / スーパーオキシド / 人工SOD / オリゴ糖錯体
Research Abstract	金属イオンと配位子との結合に多重相互作用を加えることにより,種々の金属タンパク質の機能を化学的に構築し,新しい反応系の開発を目的とし,以下の成果を得た。〔Mo_2Fe_6S_8(SEt)_9〕^<3->を触媒とするRC(O)SR'へのCO_2固定反応によりアミノ酸前駆体としてのRC(O)COOHの触媒的な生成に成功し,CO_2が〔Mo_2Fe_6S_8(SEt)_9〕^<5->の骨格イオウ上で活性化を受けて反応が進行する機構を提出した。複核銅含有のオキシヘモシアニンおよびオキシチロシナーゼの決定的な構造モデルとなる酸素錯体の合成に成功するとともに,これらの酸素錯体を用いたフェノール誘導体の酸化反応を行ない,チロシナーゼの作用機構に関して,従来の定説を覆す新しいラジカル性の反応機構を提唱した。一方,アルキル置換ヒドロキノンをプロトンおよび電子供与体とした鉄カテコール錯体を用いたオキシゲナーゼ型酸素化反応を開発し,広範囲の芳香属および直鎖飽和炭化水素からアルコール,ケトン,アルデヒドが生成することを明らかにした。生体内酸素毒性防御の観点からスーパーオキシド不均化酵素(SOD)活性を有する新規鉄錯体を十数種合成した。これらの錯体は現在報告されている人工SODの中でも最高の活性を示した。このような活性を有する錯体は前例がなく,作用機構の解明および医学への応用に興味がもたれる。グリシンの前駆体であるα-アミノマロン酸とCo(III)ポリアミン錯体との反応では溶媒の違いによりポリアミン,カルビノールアミン,α-ジアミン錯体等種々の生成物を与える。これらの反応性に関して極低温ESR,X線構造解析,理論計算等によりその生成機構を提案した。二糖類(D-Maltose,D-Melibose,D-Lactose,D-Cellobiose)を用いたNi(II)錯体の合成を行ない,X線構造解析により分子識別能を有するオリゴ糖錯体の可能性を示した。

Research Products
(29 results)

All Other

All Publications (29 results)

[Publications] H.Tanaka: "Synthesis and Characterization of Bis(2,2'-bipyridine)nitrocarbonylruthenium(II)Hexsafluorophoshate." Inorg.Chem.31. 1971-1973 (1992)
[Publications] H.Tanaka: "Crystal Structure of cis-(Carbon monoxide)(η1-carbon dioxide)bis(2,2'-bipyridine)ruthenium,an Active Speciesin Catalytic CO_2 Reduction Affording CO and HCOO^-." Organometallics. 11. 1450-1451 (1992)
[Publications] H.Tanaka: "Structure and Bonding of cis-[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN(bpy=2,2'-bipyridine)" Organometallics. 11. 3171-3172 (1992)
[Publications] N.Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->." J.Am.Chem.Soc.114. 3625-3630 (1992)
[Publications] H.Kambayashi: "(Ph_4As)_2[Fe_4S_4(SAd)_4]and Stabilization of [Fe_4S_4(SAd)_4]^- Site in Aqueous Media." Chem.Lett.919-922 (1992)
[Publications] H.Tanaka: "Comparative Study on Crystal Structures of [Ru(bpy)_2(CO)_2]PF_6,[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN,and [Ru(bpy)_2(CO)(η^1-CO_2)]・3H_2O(bpy=2,2'-bipyridyl)" Inorg.chem.
[Publications] H.Tanaka: "Evaluation of Acidity of CO_2 in Protic Media.Carboxylation of Reduced Quinone." Chem.Lett.
[Publications] T.Tanase: "A Spontaneous Fixation of Carbon Dioxide in Air by a Nickel Diamine Complex:Synthesis and Characterization of a Trinuclear Nichel(II)Complex with a Novel Hydrogen Bonding System around Carbonate Ligand." Inorg.chem.31. 1058-1062 (1992)
[Publications] T.Tanase: "C-2 Epimerization of Aldoses Promoted by Cobalt(II)-N-Alkylated Diamine Complexes,Involving a Stereospecific Rearrangement of the Carbon Skeleton." J.Chem.Res.252-253 (1992)
[Publications] T.Murata: "Synthesis of Mixed-Metal Sulfido Clusters with Cuboidal Mo_3PdS_4Core which Coordinate Alkene to the Unique Pd Site Surrounded by Sulfide Ligands." J.Am.Chem.Soc.8287-8288 (1992)
[Publications] Y.Abe: "High Dioxygen Uptake by Hetero-Metal Binuclear Co(II)-Fe(II)-schiff Base Complexes Systems in Dimethyl Sulfoxide." Chem.Lett.897-900 (1992)
[Publications] T.Kojima: "Observation of Radical intermediates for Unusual C-N Bond Formation of α-Aminomalonate to Give α-Diamine Linkage.ESR Studies on Electron Transfer Reactionsin Co(III)-Polyamine Complexes." Inorg.Chem.
[Publications] S.Yano: "Stereochemistry of Sugar Units Contained in N-Glycoside Ligands of Octahedral Ni(II)Complexes Derived form[Ni(tn)_3]^<2+> and Natural Aldohexoses." J.Chem.Soc.,Dalton Trans.
[Publications] N.Kitajima: "A New Model for Dioxygen Binding in Hemocyanin.Synthesis,Characterization,and Molecular Structure of the μ-η^2:η^2 Peroxo Dinuclear Copper(II)Complexes,[Cu(HB(3,5-R_2pz)_3]_2(O_2)(R=iPrandPh)" J.Am.Chem.Soc.114. 1277-1291 (1992)
[Publications] S.Hikichi: "Phosphate Ester Cleavage with a Zinc Hydroxide Complex.Formation and Crystal Structure of a Dineclear Zinc Complex Bridged with a Phosphate Monoester." J.Chem.Soc.,Chem.Commun.814-815 (1992)
[Publications] N.Kitajima: "Synthesis and Molecular Structure of Diferrous Complexes Containing a Bis(hydroxo)or a Hydroxo Carboxylato Bridge." Inorg.Chem.31. 3342-3343 (1992)
[Publications] N.Kitajima: "Synthesis and Characterization of Copper Complexes with Hindered Tris(pyrazolyl)borate Ligands as Models for the Active Sites of Copper Proteins." J.Inorg.Biochem.,. 47. 17 (1992)
[Publications] N.Kitajima: "Synthetic Approach to the Dioxygen Binding Sites in Metalloproteins." J.Mol Catal.,. 74. 143-151 (1992)
[Publications] N.Kitajima: "X-Ray Structure of Thiolate Copper(II)Complexes Bearing Close Spectroscopic Similarities to Blue Copper Proteins." J.Am.Chem.Soc.114. 9232-9233 (1992)
[Publications] M.J.Baldwin: "Spectroscopic Studies of Side-on Peroxo-Bridged Binuclear Copper(II)Model Complexes of Relevance to Oxyhemocyanin and Oxytyrosinase." J.Am.Chem.Soc.114. 10421-10431 (1992)
[Publications] N.Kitajima: "Synthesis and Molecular Structure of an Unsymmetric Dimanganese(II)Carboxylato Complex." J.Chem.Soc.,Chem.Commun.
[Publications] N.Kitajima: "Synthetic Approach to the Structures and Functions of Copper Proteins." Inorg.Chem.
[Publications] N.Kitajima: "Synthesis,Structure and Properties of μ-μ_2:μ_2 Peroxo Dinuclear Copper Complex.Modeling the Active Site of Oxyhemocyanin and Oxytyrosinase." Bioinorganic Chemistry of Copper.
[Publications] 北島信正: "銅蛋白質の活性部位の合成モデル錯体" 季刊化学総説、生物無機化学の新展開.
[Publications] 船引卓三: "非ヘム鉄タンパク質の合成モデル" 季刊化学総説、生物無機化学の新展開.
[Publications] T.Funabiki: "Chracteristic Effect of Pyridine on the NIH Shift and Selectivity in the Monoxygenation of Aromatic Compounds Catalyzed by a Nonheme Iron Complex/Hydroquinones/O2 System." Chem.Lett.1279-1282 (1992)
[Publications] T.Funabiki: "Controlled Monoxygenation of n-and Isoalkanes with Molecular Oxygen Catalyzed in Nonheme Iron Complex/hydroquinones Systems." Chem.Lett.2303-2306 (1992)
[Publications] 長野哲雄: "人工SODーその開発的前線ー" SODの基礎と臨床. 62-67 (1992)
[Publications] 長野哲雄: "Superoxide dismutase mimicsの分子設計" フリーラジカルと病態:疾患モデルからベッザサイドへ. 717-728 (1992)

1992 Fiscal Year Annual Research Report

生体系複合場金属錯体による新反応系の構築

Principal Investigator

田中 晃二 岡崎国立共同研究機構, 分子科学研究所, 教授 (00029274)

Research Products

[Publications] H.Tanaka: "Synthesis and Characterization of Bis(2,2'-bipyridine)nitrocarbonylruthenium(II)Hexsafluorophoshate." Inorg.Chem.31. 1971-1973 (1992)

[Publications] H.Tanaka: "Crystal Structure of cis-(Carbon monoxide)(η1-carbon dioxide)bis(2,2'-bipyridine)ruthenium,an Active Speciesin Catalytic CO_2 Reduction Affording CO and HCOO^-." Organometallics. 11. 1450-1451 (1992)

[Publications] H.Tanaka: "Structure and Bonding of cis-[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN(bpy=2,2'-bipyridine)" Organometallics. 11. 3171-3172 (1992)

[Publications] N.Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->." J.Am.Chem.Soc.114. 3625-3630 (1992)

[Publications] H.Kambayashi: "(Ph_4As)_2[Fe_4S_4(SAd)_4]and Stabilization of [Fe_4S_4(SAd)_4]^- Site in Aqueous Media." Chem.Lett.919-922 (1992)

[Publications] H.Tanaka: "Comparative Study on Crystal Structures of [Ru(bpy)_2(CO)_2]PF_6,[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN,and [Ru(bpy)_2(CO)(η^1-CO_2)]・3H_2O(bpy=2,2'-bipyridyl)" Inorg.chem.

[Publications] H.Tanaka: "Evaluation of Acidity of CO_2 in Protic Media.Carboxylation of Reduced Quinone." Chem.Lett.

[Publications] T.Tanase: "A Spontaneous Fixation of Carbon Dioxide in Air by a Nickel Diamine Complex:Synthesis and Characterization of a Trinuclear Nichel(II)Complex with a Novel Hydrogen Bonding System around Carbonate Ligand." Inorg.chem.31. 1058-1062 (1992)

[Publications] T.Tanase: "C-2 Epimerization of Aldoses Promoted by Cobalt(II)-N-Alkylated Diamine Complexes,Involving a Stereospecific Rearrangement of the Carbon Skeleton." J.Chem.Res.252-253 (1992)

[Publications] T.Murata: "Synthesis of Mixed-Metal Sulfido Clusters with Cuboidal Mo_3PdS_4Core which Coordinate Alkene to the Unique Pd Site Surrounded by Sulfide Ligands." J.Am.Chem.Soc.8287-8288 (1992)

[Publications] Y.Abe: "High Dioxygen Uptake by Hetero-Metal Binuclear Co(II)-Fe(II)-schiff Base Complexes Systems in Dimethyl Sulfoxide." Chem.Lett.897-900 (1992)

[Publications] T.Kojima: "Observation of Radical intermediates for Unusual C-N Bond Formation of α-Aminomalonate to Give α-Diamine Linkage.ESR Studies on Electron Transfer Reactionsin Co(III)-Polyamine Complexes." Inorg.Chem.

[Publications] S.Yano: "Stereochemistry of Sugar Units Contained in N-Glycoside Ligands of Octahedral Ni(II)Complexes Derived form[Ni(tn)_3]^<2+> and Natural Aldohexoses." J.Chem.Soc.,Dalton Trans.

[Publications] N.Kitajima: "A New Model for Dioxygen Binding in Hemocyanin.Synthesis,Characterization,and Molecular Structure of the μ-η^2:η^2 Peroxo Dinuclear Copper(II)Complexes,[Cu(HB(3,5-R_2pz)_3]_2(O_2)(R=iPrandPh)" J.Am.Chem.Soc.114. 1277-1291 (1992)

[Publications] S.Hikichi: "Phosphate Ester Cleavage with a Zinc Hydroxide Complex.Formation and Crystal Structure of a Dineclear Zinc Complex Bridged with a Phosphate Monoester." J.Chem.Soc.,Chem.Commun.814-815 (1992)

[Publications] N.Kitajima: "Synthesis and Molecular Structure of Diferrous Complexes Containing a Bis(hydroxo)or a Hydroxo Carboxylato Bridge." Inorg.Chem.31. 3342-3343 (1992)

[Publications] N.Kitajima: "Synthesis and Characterization of Copper Complexes with Hindered Tris(pyrazolyl)borate Ligands as Models for the Active Sites of Copper Proteins." J.Inorg.Biochem.,. 47. 17 (1992)

[Publications] N.Kitajima: "Synthetic Approach to the Dioxygen Binding Sites in Metalloproteins." J.Mol Catal.,. 74. 143-151 (1992)

[Publications] N.Kitajima: "X-Ray Structure of Thiolate Copper(II)Complexes Bearing Close Spectroscopic Similarities to Blue Copper Proteins." J.Am.Chem.Soc.114. 9232-9233 (1992)

[Publications] M.J.Baldwin: "Spectroscopic Studies of Side-on Peroxo-Bridged Binuclear Copper(II)Model Complexes of Relevance to Oxyhemocyanin and Oxytyrosinase." J.Am.Chem.Soc.114. 10421-10431 (1992)

[Publications] N.Kitajima: "Synthesis and Molecular Structure of an Unsymmetric Dimanganese(II)Carboxylato Complex." J.Chem.Soc.,Chem.Commun.

[Publications] N.Kitajima: "Synthetic Approach to the Structures and Functions of Copper Proteins." Inorg.Chem.

[Publications] N.Kitajima: "Synthesis,Structure and Properties of μ-μ_2:μ_2 Peroxo Dinuclear Copper Complex.Modeling the Active Site of Oxyhemocyanin and Oxytyrosinase." Bioinorganic Chemistry of Copper.

[Publications] 北島 信正: "銅蛋白質の活性部位の合成モデル錯体" 季刊化学総説、生物無機化学の新展開.

[Publications] 船引 卓三: "非ヘム鉄タンパク質の合成モデル" 季刊化学総説、生物無機化学の新展開.

[Publications] T.Funabiki: "Chracteristic Effect of Pyridine on the NIH Shift and Selectivity in the Monoxygenation of Aromatic Compounds Catalyzed by a Nonheme Iron Complex/Hydroquinones/O2 System." Chem.Lett.1279-1282 (1992)

[Publications] T.Funabiki: "Controlled Monoxygenation of n-and Isoalkanes with Molecular Oxygen Catalyzed in Nonheme Iron Complex/hydroquinones Systems." Chem.Lett.2303-2306 (1992)

[Publications] 長野 哲雄: "人工SODーその開発的前線ー" SODの基礎と臨床. 62-67 (1992)

[Publications] 長野 哲雄: "Superoxide dismutase mimicsの分子設計" フリーラジカルと病態:疾患モデルからベッザサイドへ. 717-728 (1992)

田中晃二岡崎国立共同研究機構, 分子科学研究所, 教授 (00029274)

[Publications] 北島信正: "銅蛋白質の活性部位の合成モデル錯体" 季刊化学総説、生物無機化学の新展開.

[Publications] 船引卓三: "非ヘム鉄タンパク質の合成モデル" 季刊化学総説、生物無機化学の新展開.

[Publications] 長野哲雄: "人工SODーその開発的前線ー" SODの基礎と臨床. 62-67 (1992)

[Publications] 長野哲雄: "Superoxide dismutase mimicsの分子設計" フリーラジカルと病態:疾患モデルからベッザサイドへ. 717-728 (1992)