1991 Fiscal Year Annual Research Report

新規ポリポプチド金属錯体の構造と触媒作用

Research Project

Project/Area Number	03241217
Research Institution	Osaka University
Principal Investigator	福住俊一大阪大学, 工学部, 助手 (40144430)
Keywords	触媒作用 / 電子移動 / 金属錯体
Research Abstract	生体類似ポリペプチド金属錯体の効率的な電子伝達を設計する上で電子移動に対する在媒作用が最も重要な問題となる。本年度の研究では電子移動に対する金属錯体の触媒作用に関する研究を行い、その触媒作用機構には基本的に以下の3つのタイプがあることを明らかにした。 1.電子キャリアとしての触媒作用ーMeCN1HClO_4が存在すると、NAD二量体モデルのアクリジンダイマ-[(AcrH)_2]はCoTPP^+/CoTPPを電子キャリアとして酸素分子へ電子伝達を行うことができることを見い出した。素過程についてMarc/s理論に基づいて詳しい速度論的解析を行った結果、(AcrH)_2からCoTPP^+への電子移動は両者の相互作用がほとんどない外圏型、CoTPPからO_2への酸在媒電子移動は相互作用の強い内圏型で進行することがわかった。この場合金属ポルフィリンにO_2が配位できることが、電子移動触媒として有効の機能する上で重要である。 2.1電子還元体との錯形成による触媒作用ー脱酸素MeCN中pーベンゾキノン類(Q)のラジカルアニオン(Q^-・)はMg^<2+>と1:1(Q^-・-Mg^<2+>),1:2(Q^-・-2Mg^<2+>)の錯体を形成することがわかった。この一電子還元体との錯形成は電子移動触媒作用の中でも最も一般的に様式であると考えられる。また。NADH類縁体による種々の基質の酵素類似還元反応における金属イオンの触媒作用も、このような一電子還元体との錯形成による電子移動触媒作用によることを明らかにした。 2ー3.ラジカル種を介する触媒作用ールイス酸金属錯体(SnCl_4,Et_3SiClO_4など)を電子移動還元すると金属中心ラジカルが生成する。αーエノン(R^1COC=CR^2R^3)存在下でケテンシリルアセタ-ル(R^4R^5C=C(OEt)OSiEt_3)により金属錯体が電子移動還元されると、金属中心ラジカルがαーエノンに付加し、ケテンシリルアセタ-ルラジカルカチオンとカップリングすることにより通常の方法では合成困難な4級炭素ー炭素結合を効率良く生成することに成功した。この場合、ラジカルを介して電子移動過程が触媒されることになる。

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] S.Fukuzumi: "Electronーtransfer Reactions from Hydroquinone Derivatives to 10ーMethylacridinium Ion in the Presence of Hydroxide Ion in Acetonitrile" Bulletin of the Chemical Society of Japan. 65. 715-719 (1992)
[Publications] S.Fukuzumi: "Selective SixーElectron Photoreduction of Nitrobenzene Derivatives by 10ーMethylー9,10ーdihydroacridine in the Presence of Perchloric Acid" Bulletin of the Chemical Society of Japan. 65. (1992)
[Publications] S.Fukuzumi: "Quinone/Hydroxide Ion Induced Oxygenation of pーBenzoquinone to Rhodizonatイ Dianion (C_6O_6^<2->),Accompanied by the OneーElectron Reduction to Semiquinone Radical Anion" Journal of the American Chemical Society. 113. 7764-7765 (1991)
[Publications] T.Sato: "Importance of Lewis AcidーMediated Electron Transfer in MukaiyamaーMichael Reaction of Ketene Silyl Acetals" Journal of the American Chemical Society. 113. 4028-4030 (1991)
[Publications] S.Fukuzumi: "10ーMethylacridine Dimer Acting as a Unique Electron Sourcc Compared to the Corresponding Monomer for the Efficient Reduction of Dioxygen,Catalysed by a Cobalt Porphyrin in the Presence of Perchloric Acid" Journal of the Chemical Society,Perkin Tranasction2. 1607-1611 (1991)
[Publications] "Multiーelectron Reduction of Nitrobenzene Dcrivatives by an Acidーstable NADH Analogue via Acidーcatalysed Electronーtransfer Radicalーchain Reactions" Journal of the Chemical Society,Perkin Transaction2. 1393-1398 (1991)
[Publications] J.Otera: "Activation of Ketene Silyl Acetals by 10ーMechylacridinium Perchlorate:A Novel Catalysis in Mukaiyama Reaction" Tetrahedron Letters. 32. 2405-2408 (1991)
[Publications] S.Fukuzumi: "Reactivities of Carbonyl Compounds in AcidーCatalyzed Hydride Transfer vs.Electron Transfer" Chemistry Letters. 2059-2062 (1991)
[Publications] S.Fukuzumi: "Autocatalytic Reduction of Nitric Acid by an Acidーstable NADH Analogue via Novel Chain Reactions" Chemistry Letters. 1913-1916 (1991)
[Publications] S.Fukuzumi: "10,10'ーDimethylー9,9'ーbiacridine Acting as a Novel Organic OuterーSphere ElectronーTransfer Reagent" Chemistry Letters. 1909-1912 (1991)
[Publications] S.Fukuzumi: "Photoinduced Cleavage of the CーC Bonds of 9ーAlkylー10ーmethylー9,10ーdihydroacridines by Perchloric Acid" Chemistry Letters. 1905-1908 (1991)
[Publications] S.Fukuzumi: "Formation of Proton Gradients in Electron Transport between Two ProtonーConducting Acetonitrile Phases Separated by an Insulating Carbon Disulfide Phase" Chemistry Letters. 1835-1838 (1991)
[Publications] S.Fukuzumi: "AcidーCatalyzed Photoreduction of Dialkyl Sulfoxides by an AcidーStable NADH Analogue" Chemistry Letters. 897-900 (1991)
[Publications] S.Fukuzumi: "Mechanisms of Reductive Methylation of NAD^+ Analogues by a transーDimethylーcobalt(III) Complex" Journal of the Chemical Society,Perkin Transaction2. 41-45 (1991)
[Publications] S.Fukuzumi: "Advances in Electron Transfer Chemistry" JAI Press, 109 (1992)
[Publications] S.Fukuzumi: "Trends in Organic Chemistry" Council of Scientific Research Integration, 24 (1992)

1991 Fiscal Year Annual Research Report

新規ポリポプチド金属錯体の構造と触媒作用

Principal Investigator

福住 俊一 大阪大学, 工学部, 助手 (40144430)

Research Products

[Publications] S.Fukuzumi: "Electronーtransfer Reactions from Hydroquinone Derivatives to 10ーMethylacridinium Ion in the Presence of Hydroxide Ion in Acetonitrile" Bulletin of the Chemical Society of Japan. 65. 715-719 (1992)

[Publications] S.Fukuzumi: "Selective SixーElectron Photoreduction of Nitrobenzene Derivatives by 10ーMethylー9,10ーdihydroacridine in the Presence of Perchloric Acid" Bulletin of the Chemical Society of Japan. 65. (1992)

[Publications] S.Fukuzumi: "Quinone/Hydroxide Ion Induced Oxygenation of pーBenzoquinone to Rhodizonatイ Dianion (C_6O_6^<2->),Accompanied by the OneーElectron Reduction to Semiquinone Radical Anion" Journal of the American Chemical Society. 113. 7764-7765 (1991)

[Publications] T.Sato: "Importance of Lewis AcidーMediated Electron Transfer in MukaiyamaーMichael Reaction of Ketene Silyl Acetals" Journal of the American Chemical Society. 113. 4028-4030 (1991)

[Publications] "Multiーelectron Reduction of Nitrobenzene Dcrivatives by an Acidーstable NADH Analogue via Acidーcatalysed Electronーtransfer Radicalーchain Reactions" Journal of the Chemical Society,Perkin Transaction2. 1393-1398 (1991)

[Publications] J.Otera: "Activation of Ketene Silyl Acetals by 10ーMechylacridinium Perchlorate:A Novel Catalysis in Mukaiyama Reaction" Tetrahedron Letters. 32. 2405-2408 (1991)

[Publications] S.Fukuzumi: "Reactivities of Carbonyl Compounds in AcidーCatalyzed Hydride Transfer vs.Electron Transfer" Chemistry Letters. 2059-2062 (1991)

[Publications] S.Fukuzumi: "Autocatalytic Reduction of Nitric Acid by an Acidーstable NADH Analogue via Novel Chain Reactions" Chemistry Letters. 1913-1916 (1991)

[Publications] S.Fukuzumi: "10,10'ーDimethylー9,9'ーbiacridine Acting as a Novel Organic OuterーSphere ElectronーTransfer Reagent" Chemistry Letters. 1909-1912 (1991)

[Publications] S.Fukuzumi: "Photoinduced Cleavage of the CーC Bonds of 9ーAlkylー10ーmethylー9,10ーdihydroacridines by Perchloric Acid" Chemistry Letters. 1905-1908 (1991)

[Publications] S.Fukuzumi: "Formation of Proton Gradients in Electron Transport between Two ProtonーConducting Acetonitrile Phases Separated by an Insulating Carbon Disulfide Phase" Chemistry Letters. 1835-1838 (1991)

[Publications] S.Fukuzumi: "AcidーCatalyzed Photoreduction of Dialkyl Sulfoxides by an AcidーStable NADH Analogue" Chemistry Letters. 897-900 (1991)

[Publications] S.Fukuzumi: "Mechanisms of Reductive Methylation of NAD^+ Analogues by a transーDimethylーcobalt(III) Complex" Journal of the Chemical Society,Perkin Transaction2. 41-45 (1991)

[Publications] S.Fukuzumi: "Advances in Electron Transfer Chemistry" JAI Press, 109 (1992)

[Publications] S.Fukuzumi: "Trends in Organic Chemistry" Council of Scientific Research Integration, 24 (1992)

福住俊一大阪大学, 工学部, 助手 (40144430)