Catalytic Control of Diels-Alder Reaction via Photoinduced Electron Transfer

• Project/Area Number: 09450318
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: 工業物理化学
• Research Institution: Osaka University
• Principal Investigator: FUKUZUMI Shunichi Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (40144430)
• Co-Investigator(Kenkyū-buntansha): SUENOBU Tomoyoshi Osaka University, Graduate School of Engineering, Assistant Professor, 大学院・工学研究科, 助手 (90271030) ; ITOH Shinobu Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (30184659)
• Project Period (FY): 1997 – 1998
• Project Status: Completed (Fiscal Year 1998)
• Budget Amount: ¥13,800,000 (Direct Cost: ¥13,800,000); Fiscal Year 1998: ¥2,000,000 (Direct Cost: ¥2,000,000); Fiscal Year 1997: ¥11,800,000 (Direct Cost: ¥11,800,000)
• Keywords: Catalysis / Potoinduced Electron Transfer / Diels-Alder Reaction / Scandium Ion / Redox Reaction / Excited State / 光Diels-Alder反応 / 電子移動 / 位置選択性の制御 / アントラセン類 / ビニルケトン類 / 反応機構 / 光電子移動 / 触媒 / 反応制御 / 還化付加反応 / 炭素-炭素結合生成 / 位置異性体

Research Abstract

Photochemical reactions involving photo-excited states can also be catalyzed as well as the thermal reactions of ground states. However, the lifetimes of excited sates are usually very short and accordingly any reaction of the excited state should be fast enough to compete the decay of the excited state to the ground state. Thus, there seems to be little chance of a catalyst to accelerate further the reactions of excited states, which are already fast. The reactivity of photoinduced electron transfer is automatically determined F once the pair of electron donor and acceptor, one of which is an excited state, is fixed. The excited state may have an energetically favorable electron transfer pathway with a substrate, otherwise the reaction would have no chance to compete with fast physical decay to the ground state (typically the lifetime is 10^<-6> to 10^<-12> s). Despite these apparent difficulties, we have developed a number of examples of photochemical reactions including Diels-Alder reactions that involve catalyzed electron transfer processes as the rate-determining steps. Fundamental concepts for catalysis of photoinduced electron transfer reactions have been established and photochemical redox reactions which would. otherwise be unlikely to occur are made possible to proceed efficiently by applying the catalysis on the photoinduced electron transfer steps.

Research Products

• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Properties of C_<60> and tert-Butyl-C_<60> Radical" J.Am.Chem.Soc.121・(in press). (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "ESR Spectra of Superoxide Anion-Scandium Complexes Detectable in Fluid Solution" J.Am.Chem.Soc.121・7. 1605-1606 (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Kinetics for Generation of Organoiron(IV)Porphyrins and the Iron(IV)Porphyrin π Radical Cations" J.Am.Chem.Soc.121・4. 785-790 (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortions of the Macrocycle" Angew.Chem.111・. in press- (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Selective One-Electron and Two-Electron Reduction of C_<60> with NADH and NAD Dimer Analogues via Photoinduced Electron Transfer" J.Am.Chem.Soc.120・32. 8060-8068 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Formation of Radical Anion in the Reaction of p-Benzoquinone and C_<60> with Alkoxide Ions" J.Am.Chem.Soc.120・27. 6673-6680 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Mechanisms of N-Demethylations Catalyzed by High Valent Intermediates of Heme Enzymes : Novel Isotope Effect Determination by Direct Observation of Intermediates in N-Demethylation Reactions" J.Am.Chem.Soc.120・41. 10762-10763 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Formation of C_<60> Adducts with Two Different Alkyl Groups via Combination of Electron Transfer and S_N2 Reactions" J.Am.Chem.Soc.121・36. 9220-9227 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Mechanism of Organocobalt Porphyrins. Site of Electron Transfer,Migration of Organic Groups,and Cobalt-Carbon Bond Energies in Different Oxidation States" J.Am.Chem.Soc.121・12. 2880-2889 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Direct Observation of Radical Intermediates While Investigating the Redox Behavior of Thiamin Coenzyme Models" Angew.Chem.110・7. 1040-1042 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Synthesis and Spectroscopic and Electrochemical Characterization of Di-and Tetrasubstituted C_<60> Derivatives" J.Phys.Chem.A. 102・22. 3898-3906 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Kinetic and Thermodynamic Studies of Iron(III) and Iron(IV) Sigma Bonded Porphyrins. Formation and Reactivity of〔(OEP)Fe(R)〕^<n+> where OEP is the Dianion of Octaethylporphyrin,n=0,1,2,3 and R=C_6H_5,3,4,5-C_6F_3H_2,2,4,6-C_6F_3H_2,C_6F_4H or C_6F_5," Inorg.Chem.37・8. 1759-1766 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi et al.: "Advances in Photochemistry" Wiley, 107-172 (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shunichi Fukuzumi, Ikuo Nakanishi, Tomoyoshi: "Suenobu, and Karl M.KadishElectron-Transfer Properties of C_<60> and tert-Butyl-C_<60> Radical" J.Am.Chem.Soc.121, (in press). (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Ikuo Nakanishi, Keiko Tanaka, Tomoyoshi Suenobu, Alain Tabard, Roger Guilard, Eric Van Caemelbecke, and Karl M.Kadish: "Electron Transfer Kinetics for Generation of Organoiron (IV) Porphyrins and the Iron(IV) Porphyrin pi Radical Cations" J.Am.Chem.Soc.121. 785-790 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Matthias Patz, Tomoyoshi Suenobu, Yoshihiro Kuwahara, and Shinobu Itoh: "ERS Spectra of Superoxide Anion-Scandium Complexes Detectable in Fluid Solution" J.Am.Chem.Soc.121. 1605-1606 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Ikuo Nakanishi, Jean-Michel Barbe, Roger Guilard, Eric Van Caemelbecke, Ning Guo, and Karl M.Kadish: "Slowing of Electron Transfer Rates of Manganese Porphyrins due to Conformational Distortions of the Porphyrin Ring" Angew.Chem., 111 ; Angew.Chem., Int.Ed.Engl.38(in press). (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Yoshio Goto, Yoshihito Watanabe, Shunichi Fukuzumi, Jeffry P.Jones, and Joseph P.Dinnocenzo: "The Mechanisms of N-Demethylation Catalyzed by Heme Enzymes : Direct Observation of N-Demethylation by Compound I of Horseradish Peroxidase and Its Model Complex" J.Am.Chem.Soc.120. 10762-10763 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Tomoyoshi Suenobu, Takeomi Hirasaka, Ryuichi Arakawa, and Karl M.Kadish: "Formation of C_<60> Adducts with Two Different Alkyl Groups via Combination of Electron Transfer and SN2 Reactions" J.Am.Chem.Soc.120. 9220-9227 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Tomoyoshi Suenobu, Matthias Patz, Takeomi Hirasaka, Shinobu Itoh, Mamoru Fujitsuka, and Osamu Ito: "Selective One-Electron and Two-Electron Reduction of C_<60> with NADH and NAD Dimer Analogs via Photoinduced Electron Transfer" J.Am.Chem.Soc.120. 8060-8068 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shinobu Itoh, Hirokatsu Kawakami, and Shunichi Fukuzumi: "Electrochemical Behavior and Characterization of Semiquinone Radical Anion Species of Coenzyme PQQ in Aprotic Organic Media" J.Am.Chem.Soc.120. 7271-7277 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Ikuo Nakanishi, Junichi Maruta, Tomohiro Yorisue, Tomoyoshi Suenobu, Shinobu Itoh, Ryuichi Arakawa, and Karl M.Kadish: "Formation of Radical Anions in the Reactions of p-Benzoquinones and C_<60> with Alkoxide Ions" J.Am.Chem.Soc.120. 6673-6680 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi, Kenichi Miyamoto, Tomoyoshi Suenobu, Eric Van Caemelbecke, and Karl M.Kadish: "Electron Transfer Mechanism of Organocobalt Porphyrins. Site of Electron Transfer, Migration of Organic Groups, and Cobalt-Carbon Bond Energies in Different Oxidatin States" J.Am.Chem.Soc.120. 2880-2889 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Properties of C_<60> and tert-Butyl-C_<60> Radical" J.Am.Chem.Soc.121・(in press). (1999)
• [Publications] Shunichi Fukuzumi et al.: "ESR Spectra of Superoxide Anion-Scandium Complexes Detectable in Fluid Solution" J.Am.Chem.Soc.121・7. 1605-1606 (1999)
• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Kinetics for Generation of Organoiron(IV)Porphyrins and the Iron(IV)Porphyrin π Radical Cations" J.Am.Chem.Soc.121・4. 785-790 (1999)
• [Publications] Shunichi Fukuzumi et al.: "Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortions of the Macrocycle" Angew.Chem.111・(in press). (1999)
• [Publications] Shunichi Fukuzumi et al.: "Selective One-Electron and Two-Electron Reduction of C_<60> with NADH and NAD Dimer Analogues via Photoinduced Electron Transfer" J.Am.Chem.Soc.120・32. 8060-8068 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Formation of Radical Anion in the Reaction of p-Benzoquinone and C_<60> with Alkoxide Ions" J.Am.Chem.Soc.120・27. 6673-6680 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Mechanisms of N-Demethylations Catalyzed by High Valent Intermediates of Heme Enzymes: Novel Isotope Effect Determination by Direct Observation of Intermediates in N-Demethylation Reactions" J.Am.Chem.Soc.120・41. 10762-10763 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Formation of C_<60> Adducts with Two Different Alkyl Groups via Combination of Ekectron Transfer and S_N2 Reactions" J.Am.Chem.Soc.121・36. 9220-9227 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Mechanism of Organocobalt Porphyrins,Site of Electron Transfer,Migration of Organic Groups,and Cobalt-Carbon Bond Energies in Different Oxidation States" J.Am.Chem.Soc.121・12. 2880-2889 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Direct Observation of Radical Intermediates While Investigating the Redox Behavior of Thiamin Coenzyme Models" Angew.Chem.110・7. 1040-1042 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Synthesis and Spectroscopic and Electrochemical Characterization of Di-and Tetrasubstituted C_<60> Derivatives" J.Phys.Chem.A. 102・22. 3898-3906 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Kinetic and Thermodynamic Studies of Iron(III)and Iron(IV)Sigma Bonded Porphyrins.Formation and Reactivity of [(OEP)Fe(R)]^<n+> where OEP is the Dianion of Octaethylporphyrin,n=0,1,2,3 and R=C_6H_5,3,4,5-C_6F_3H_2,2,4,6-C_6F_3H_2,C_6F_4H or C_6F_5," Inorg.Chem.37・8. 1759-1766 (1998)
• [Publications] Shunichi Fukuzumi et al.: "Advances in Photochemistry" Wiley, 107-172 (1999)
• [Publications] Shunichi Fukuzumi et al.: "Electron Transfer Mechanism of Organocobalt Porphyrins. Site of Electron Transfer,Migration of Organic Groups, and Cobalt-Carbon Bond Energies in Different Oxidation States" J. Am. Chem. Soc.(印刷中). (1998)
• [Publications] Shunichi Fukuzumi et al.: "Kinetic and Thermodynamic Studies of Iron(III) and Iron(IV) Sigma Bonded Porphyrins. Formation and Reactivity of [(OEP)Fe(R)]^<n1> where OEP is the Dianion of Octaethylporphyrin,n=0,1,2,3 and R=C_6H_5,3,4,5-C_6F_3H_2,2,4,6-C_6F_3H_2,C_6F_4HorC_6F_5" Inorg. Chem.(印刷中). (1998)
• [Publications] Shunichi Fukuzumi et al.: "Mechanicstic Studies of Aliphatic Ligand Hydroxylation of a Copper Complex by Dioxygen: A Model Reaction for Copper Monooxygenases" J. Am. Chem. Soc.120・(印刷中). (1998)
• [Publications] Shunichi Fukuzumi et al.: "Modeling of the Chemistry of Quinoprotein Methanol Dehydrogenase. Oxidation of Methanol by Calcium Complex of Coenzyme PQQ via Addition-Elimination Mechanism." J. Am. Chem. Soc.119・2. 439-440 (1997)
• [Publications] Shunichi Fukuzumi et al.: "Direct Observation of Radical Intermediates Derived from Thiamin Coenzyme Models and the Redox Behavior" Angew. Chem. Int. Ed.37・(印刷中). (1998)
• [Publications] Shunichi Fukuzumi et al.: "Model Studies of Calcium-containing Quinoproteins Alcohol Dehydrogenaes. Catalytic Role of Ca^<2+> for the Oxidation of alcohols by Coenzyme PQQ" Biochemistry. ・(印刷中). (1998)
• [Publications] Shunichi Fukuzumi et al.: "Advances in Photochemistry" Wiley(New York)(印刷中), (1998)