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Wada Kenji

  • Faculty of Medicine
  • School of Medicine
  • International Office
  • Professor
Last Updated :2025/04/24

Researcher Information

Degree

  • 博士（工学）（Kyoto University）
  • PhD

J-Global ID

Research Interests

  • グリーンケミストリー   触媒   医用化学   Green Chemistry   Catalysis   Chemistry for Medicine   

Research Areas

  • Energy / Earth resource engineering, energy science
  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Catalytic processes and resource chemistry
  • Life sciences / Bioorganic chemistry
  • Nanotechnology/Materials / Structural/physical organic chemistry

Academic & Professional Experience

  • 2021/04 - Today  Kagawa UniversitySpecial Assistant to the President
  • 2010 - 2013  Kyoto UniversityGraduate School of EngineeringAssociate Professor
  • 2013  Kagawa UniversityFaculty of MedicineProfessor
  • 2003 - 2010  Kyoto UniversityGraduate School of EngineeringSenior Lecturer
  • 1992 - 2003  Kyoto UniversityFaculty of EngineeringAssistant Professor

Education

  •        - 1992  Kyoto University  Graduate School, Division of Engineering
  •        - 1992  Kyoto University  工学研究科  石油化学
  •        - 1987  Kyoto University  Faculty of Engineering  Department og Hydrocarbon Chemistry
  •        - 1987  Kyoto University  Faculty of Engineering  石油化学

Association Memberships

  • アメリカ化学会   ケイ素化学協会   日本エネルギー学会   石油学会   触媒学会   日本化学会   Japan Association of Zeolite   Japan Sol-Gel Society   The Society of Silicon Chemistry Japan   Kinki Chemical Society   Japan Energy Institute   Japan Petroleum Institute   Catalysis Society of Japan   American Cjemical Society   Chemical Society of Japan   

Published Papers

Books etc

  • 触媒の設計・反応制御 事例集(分担執筆) かご状シルセスキオキサンを活かした固体触媒の調製と高活性化
    技術情報協会 2013

MISC

Industrial Property Rights

Research Grants & Projects

  • 水素社会構築と持続可能な開発目標（SDGs）達成に貢献する触媒的有機反応群の開発
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 2022/04 -2025/03 
    Author : 藤田 健一; 和田 健司; 森崎 泰弘
  • Development of catalysts for hydrogen production and environmentally benign organic synthesis by the precise control of metallic species on the specific surface sites
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2022/04 -2025/03 
    Author : 和田 健司; 馮 旗; 藤田 健一; 原 賢二
  • Mid-infrared passive spectral imaging by stealth multi-slit
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2022/04 -2025/03 
    Author : 石丸 伊知郎; 和田 健司; 岡崎 慎一郎
  • Ultrasonic-assisted mid-infrared spectroscopic imaging for non-invasive blood glucose sensor
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2018/04 -2021/03 
    Author : Ichiro ISHIMARU
     
    An ultrasonic transducer (frequency: 800 kHz, applied voltage: 10 V) was placed under the mouse ear to generate parametric standing waves. Agar was placed between the ear and the transducer as acoustic impedance matching. Mid-infrared spectroscopic measurements of reflected light from inside the ear without ultrasound applied and with ultrasonic parametric standing waves generated were compared. The glucose-induced absorption peaks (@9.25 and 9.65 micrometers) were not observed in the ultrasound-off condition. However, when ultrasonic parametric standing waves were generated, the absorption peaks were successfully and stably observed.
  • Development of environmentally benign solid catalysis based on surface dynamic organometallic chemistry
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2017/04 -2020/03 
    Author : Wada Kenji
     
    In the present study, highly-active environmentally-benign solid catalysts were developed by controlling the dynamic behaviour of organometallic species on the surface of solid crystals. Rutile-supported Ir catalysts that were effective for the synthesis of benzimidazoles via the dehydrogenative pathway were developed. For the synthesis of benzimidazoles via hydrogen transfer, the Ir catalysts supported on {010}/{101}-faceted anatase showed the excellent activity. Also, the P-modification of titania supports greatly enhanced the activity. The composite catalysts of Ir complexes and ceria that were active and selective for the dehydrogenative silylation of styrenes were developed. The treatment of Ru/CeO2 catalysts with PPh3 and HCHO was an efficient way to generate the active species for hydroarylation of C-C multiple bonds. A novel Fourier-transformed near-infrared imaging spectroscopic system that realized the rapid and direct analysis of organic products was developed.
  • Development of catalysts for organic transformations utilizing defect-rich metal oxide supports
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2013/04 -2015/03 
    Author : WADA Kenji; HOSOKAWA Saburo
     
    In the present work, solid catalysts for organic transformations have been developed using metal oxide supports with characteristic properties. Titania-supported iridium catalysts showed excellent activities for the dehydrogenative synthesis of benzimidazoles from primary alcohols and phenylenediamine derivatives under mild reaction conditions. With our catalysts, benzimidazole derivatives were selectively produced at 120 oC or lower temperatures, while the reactions with conventional ruthenium complex catalysts require a higher temperature, 200 oC. Highly-dispersed iridium nanoparticles (< 2 nm) formed on the surface of metal oxide supports are considered to be responsible for the excellent activity. In addition, hexagonal modified REFeO3 has been successfully prepared by a solvothermal method.
  • Development of environmentally-benign solid catalysts for ubiquitous green organic synthesis
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2012/04 -2015/03 
    Author : WADA Kenji; HOSOKAWA Saburo
     
    In the present study, environmentally-benign solid catalysts that enable a wide range of green organic transformation with high atom efficiency have developed. Ceria-supported ruthenium (Ru/CeO2) was found to be an effective catalyst for linear-selective dimerization of styrenes. The catalytic intermolecular hydroacylation of alkynes has been achieved in the presence of Ru catalysts. Phospine-modified ceria-supported rhodium catalysts with excellent activity in silylative coupling reactions have been also developed. On the other hand, HCHO-treated Ru/CeO2 also showed excellent activity towards the silylative coupling reaction. Towards the dehydrogenative silylation of alkenes by a hydrosilane, the combination of a small amount of Ir complexes and ceria was found to show excellent activity. In addition, metastable hexagnal iron-based mixed oxides, REFeO3, has been successfully prepared .
  • Challenge to Green Innovation by Recycling of Carbon Dioxide as an Effective Carbon Resource
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2012/04 -2014/03 
    Author : KONDO Teruyuki; WADA Kenji
     
    In this study, ruthenium-catalyzed intermolecular [2 + 2 + 1] cocyclization of ketenes, alkynes, and carbon monoxide to 2-furanones has been developed. In addition, 4(3H)-quinazolinones were obtained in high yield by catalytic N-heterocyclization of 2-aminobenzamides with formamides. It is considered that both reactions develop into the new reactions, in which carbon dioxide may be used as an effective carbon resource in the future.
  • 医学応用を指向した新しい分光分析機器の開発
    Date (from‐to) : 2013
  • Development of new spectroscopic apparatus for medicine
    Date (from‐to) : 2013
  • Preparation of Highly Active Catalysts Utilizing Synergetic Effects between Solid Surfaces and Metal Complexes
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2011 -2012 
    Author : WADA Kenji
     
    The development of novel catalysts for environmentally benign, energy-efficient organic synthetic processes is of great importance. In the present study, solid metal oxide-supported catalysts having excellent activities for the selective monoamination of 1,4-, 1,5-, and 1,6-diols by primary amines to give linear N-(hydroxyalkyl)amines have been developed. On the other hand, silicas as additives strongly promoted the epoxidation of cyclooctene by tBuOOH in the presence of Ti-silsesquioxane (Ti-POSS), where Ti species were found to be bound to the silica surface through the ligand exchange. Furthermore, highly -active silica-supported Ti catalysts were prepared by the thermal treatment of mixtures of Ti-POSS and silica.
  • Development of Novel Heterogeneous Ruthenium Catalysts for Environmentally-benign Organic Transformations
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2009 -2011 
    Author : WADA Kenji; HOSOKAWA Saburo
     
    The development of novel solid catalysts effective for environmentally benign, highly atom-efficient organic transformations is highly desired. In the present study, CeO2-or ZrO2-supported ruthenium catalysts which are quite effective for the direct arylation and alkylation of stable aromatic C-H bond activation, the allyl transfer reactions via the cleavage and reconstruction of stable C-C bonds, the regio-and stereoselective addition of carboxylic acids to alkynes, the selective cross-coupling of unsaturated hydrocarbons, and the synthesis of indole via the dehydrogenative cyclization of an amino alcohol have been developed. These catalysts are recyclable without loss of significant activities, and the leaching of Ru species into solution is negligible. The spectroscopic studies, e. g. XAFS and FTIR studies, have revealed the formation of distorted Ru=O species on the surface of ceria, which would be transformed to low-valent active Ru species in situ.
  • セリア担持酸化ルテニウム触媒を活用する環境調和型高度分子変換プロセスの開発
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 2009 -2010 
    Author : 井上 正志; 和田 健司; 細川 三郎
     
    より環境負荷の小さな有機合成プロセスの開発と、こうしたプロセスを可能にする新触媒の開発は重要な課題である。中でも不活性炭素-水素結合活性化を伴う分子変換反応は、有機合成化学における最重要課題として興味を集めているが、こうした反応については、均一系金属錯体触媒の使用が不可欠と信じられていたというのが実情である。本研究では、均一系金属錯体触媒を用いなければ達成し得なかった不活性炭素-水素結合活性化を伴う分子変換反応を対象として、錯体触媒が本質的に抱える環境上・実用上の制約を一気に解消できる、セリア担持酸化ルテニウム触媒を活用する環境調和型プロセスを構築する。 本年度は、芳香族炭素-水素結合の直接アリール化およびアルキル化反応に対する、触媒の前処理の効果を検討した。水素雰囲気下で少量のトリフェニルボスフィンとともにセリア担持酸化ルテニウム触媒を100℃程度で20分～60分間加熱したところ、これらの反応に対する活性が飛躍的に向上した。例えば、前処理なしでは反応温度170℃で24時間を要したプロモベンゼンによるベンゾ[h]キノリンの直接アリール反応が、反応温度120℃で90分以内に完結した。FTIR等による触媒の分析結果から、酸化セリウム上に歪んだ配位構造を有するRu=O種が特異的に生成し、これが前処理段階で還元されて触媒活性種が発生していると推察される。 さらに、メシチレン等のSP^3 C-H結合の活性化を伴うホウ素化反応に有効な触媒の探索を行ったところ、酸化チタン担持パラジウム触媒が特に高い活性を示すことを見出した。特に、40℃といった室温に近い反応温度でもメシチレンとビスピナコラートジボロン間の反応が円滑に進行し、ベンジル位がホウ素化された生成物が中程度の収率で得られた。
  • Creation of Innovative and Environmentally Benign Methods for Catalytic Construction of Ring Compounds via Reactive Metallacyclic Intermediates
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2008 -2010 
    Author : KONDO Teruyuki; WADA Kenji
     
    For the continuing prosperity of human society in the 21st century, it is essential to construct environmentally benign catalytic processes without byproducts and waste, directed toward organic synthesis. In the Scientific Research B, novel rhodium-catalyzed cross-coupling and cycloaddition reactions of ketenes with alkenes or alkynes have been developed, leading to efficient methods for construction of cyclopropanes, 2-pyridones, pyrimidine-2,4-diones, and furans, which constitute new and functional monomers and materials. On the other hand, we have made an important contribution to ruthenium chemistry by developing a lot of novel ruthenium-catalyzed reactions as well as creation of novel Ru (0) and Ru (II) monomers and clusters. Recently, we have succeeded in development of codimerization and cotrimerization reactions of different alkenes, and in the Scientific Research B, we found that our original ruthenium(0) complex, Ru(η^6-cot)(η^2-dmfm)_2 [cot =1,3,5-cyclooctatriene, dmfm = dimethyl fumarate], showed high catalytic activity for selective trimerization of ethylene to isohexenes. It seems that the reaction proceeds via normal and successive insertion of ethylene into an alkyl-ruthenium bond. However, the present reaction proceeded via ruthenacyclopentanes as a key intermediate, which was confirmed by the formation of unusual isohexenes (a branched cotrimer) in place of normal 1-hexene (a linear cotrimer) as well as deuterium-labeled experiments. Accordingly, the reactions developed in this Scientific Research B are all atom-economical and environmentally benign processes, which offer innovative methods for construction of ring compounds via an efficient formation of metallacyclic intermediates. As a result, this research contributes significantly to green sustainable chemistry (GSC) for organic synthesis in the 21st century.
  • Development of silsesquioxane-based novel catalysts for environmentally benign organic transformations
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2006 -2008 
    Author : WADA Kenji
     
    金属含有シルセスキオキサンの特長を生かして,制御された細孔・ビルドアップ構造を有する新しいタイプの環境対応型触媒開発を検討し,アルコールの空気酸化反応に有効なシルセスキオキサン保護パラジウムナノクラスター触媒,アルケンのヒドロホルミル化反応に有効なルテニウム種内包多孔質触媒,アルケンのエポキシ化反応に高活性を示すシリカ固定化チタン含有シルセスキオキサン触媒およびチタン含有シルセスキオキサンゲル触媒を新たに開発した.
  • Development of Methods for Novel Construction of Ring Compounds by Environmentally Benign Transition Metal Catalysts
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2006 -2007 
    Author : KONDO Teruyuki; WADA Kenji
     
    The creation of novel transition metal complexes which show high catalytic performance is essential for development of highly atom-economical and environmentally benign synthetic methods. In this study, we first succeeded in preparation of novel Ru (0) complexes bearing arenes, p-quinones, tridentate pyridyl ligands, and maleimides via selective displacement of either1,3,5-cyclooctatriene (cot) or dimethyl fumarate (dmfm) ligands in Ru (η^6-1,3,5-cyclooctatriene) (η^2-dimethyl fumarate)_2 (1). In sharp contrast, a similar Ru (0) complex, Ru (η^4-1,5-cyclooctadiene) (η^6-1,3,5-cyclooctatriene) (2) smoothly reacted with maleimides to give novel divalent ruthenacyclopentane complexes (3) via oxidative cyclization of a cot ligand and maleimides on the ruthenium, which may realize the development of novel transition-metal catalyzed [6+2] cocyclization reaction. Based on the above described stoichiometric reactions, novel methods for construction of various ring compounds using environmentally benign ruthenium and rhodium catalysts have been developed in this study. Representative examples include 1) first ruthenium-catalyzed [2+2+1] cocyclization of isocyanates, alkynes, and carbon monoxide enables the rapid synthesis of polysubstituted maleimides, 2) rhodium-catalyzed cyclocotrimerization of isocyanates and alkynes leading to the selective formation of 2-pyridones and pyrimicline-2,4-diones by controlling the molar ratio of isocyanates and alkynes, 3) rhodium-catalyzed direct synthesis of substituted phenols from cyclobutenones and electron-deficient alkenes via C-C bond cleavage/dehydrogenation, and 4) selective codimerization and cotrimerization of different alkenes, as well as selective trimerization of ethylene, via ruthenacyclic intermediates. All reactions proceed with high atom-efficiency and give functional monomers without the formation of byproducts.
  • Preparation of Novel Silsesquioxane-Based Materials with Characteristic Catalytic Functions
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2004 -2005 
    Author : WADA Kenji
     
    Caged metal-containing silsesquioxanes have attracted much attention from the viewpoint of discrete, well-defined soluble model compounds of the transition metal-containing siliceous heterogeneous catalysts. In the present work, synthesis of a series of silsesquioxanes with novel structures have been performed as well as the preparation of precursors of organic-inorganic hybrid materials for catalysts. Preparation of porous oxide catalysts utilizing silsesquioxanes was also examined. 1. Preparation of Novel Caged Silsesquioxanes The intramolecular cyclotrimerization of a half-caged silsesquixane with three ethynylsilyl groups gave novel caged silsesquioxanes composed of a siloxane framework and a 1,3,5-substituted benzene ring and a 1,2,4-substituted one in a combined yield of 52% by the reaction at 170℃ for 16 h in the presence of 15.0 mol% of CpCo(CO)_2 catalyst. 2. Synthesis of Dendritic or Starburst-type Silsesquioxanes The Pt-catalyzed hydrosilylation of octakis(dimethylsiloxy)silsesquioxane ((HSi(CH_3)_2)_8Si_8O_<12>) with ten equivalents of a silsesquloxane disilanol with a dimethylvinylsilyl group in toluene afforded a starburst-type silsesquioxane containing 16 silanol groups in 83% yield. A starburst-type silsesquioxane with sixteen Si-H groups and that bearing phenyl boryl groups have been synthesized in good yields. Further hydrosilylative reaction with a silsesquioxane bearing allylsilyl groups successfully yields the expected 2nd generation dendrimer in the yield of 63%. 3. Preparation of Porous Acidic Catalysts from Aluminosilsesquioxanes The catalytic activities of a series of porous oxides prepared from aluminosilsesquioxanes for the cracking of hydrocarbons have been examined. Among the oxides examined, the oxides prepared from aluminum-bridged silsesquioxanes show excellent catalytic activities for the cracking of cumene even at low reaction temperatures of around 523 K, indicating exceptionally high activities in spite of their amorphous nature. 4. Preparation of Palladium Oxide Nanoparticles-Encapsulating Porous Oxide Catalysts for Oxidation Utilizing a Silsesquioxane Ligand The controlled calcination of Pd complexes bearing a silsesquioxane-amine ligand at 823 K in air stream for 4 h afforded porous silicas of high surface areas and uniformly controlled micropores of ca. 0.6 nm diameter encapsulating monodispersed palladium oxide nanoparticles. The calcination after the impregnation of palladium-silsesquioxane complexes onto various supports afforded oxides with both meso- and micropores. These catalysts showed excellent catalytic activities towards the aerobic oxidation of benzyl alcohol, especially in water.
  • Creation of Novel Environmentally Benign Low-Valent Ruthenium Catalysts
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2004 -2005 
    Author : MITSUDO Take-aki; KONDO Teruyuki; WADA Kenji; URA Yasuyuki
     
    The creation of novel transition metal complexes which show high catalytic performance is essential for development of highly atom-economical and environmentally benign synthetic methods without the formation of byproducts. In this study, we first succeeded in preparation of novel Ru(0) complexes bearing arenes, p-quinones, and tridentate pyridyl ligands via selective displacement of either 1,3,5-cyclooctatriene (cot) or dimethyl fumarate (dmfm) ligands in Ru(η^6-cot)(η^2-dmfm)_2 (1). The stoichiometric reaction of 1 with phenol gave novel Ru(II) phenolate complexes, while the reaction of 1 with water in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) gave a novel chiral Ru(0) aqua complex, Ru(η^2-dppe)(η^2-dmfm)_2(H_2O) (2). The structures of all novel complexes were clearly determined by X-ray crystallography. Optical resolution of rac-2 was successfully performed by HPLC equipped with a chiral column. In addition, we have developed the following novel catalytic reactions characteristic to ruthenium ; 1)formal [4+2] cycloaddition of alkynes with electron-deficient alkenes to cyclohexenedicarboxylates via isomerization of alkynes and successive Diels-Alder reaction, 2)[2+2+2] cocyclotrimerization of three different alkynes (dimethyl acetylenedicarboxylate, 1-decyne and 3-hexyne), 3)regio- and stereoselective linear codimerization of 2-norbornenes with acrylic compounds, 4)synthesis of 2-alkylidenetetrahydrofurans by codimerization of dihydrofurans with α,β-unsaturated esters. All these ruthenium-catalyzed reactions offered the synthetic methods for novel functional monomers with high atom-efficiency.
  • Activation of Small Polar Molecules by Environmentally Benign Transition Metal Catalysts
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2003 -2005 
    Author : KONDO Teruyuki; MITSUDO Take-aki; WADA Kenji; URA Yasuyuki
     
    Since we have already found that among group 8-10 transition metal complexes, low-valent ruthenium complexes especially show high affinity to heteroatoms such as N, S, and O atoms, characteristic activation of small polar molecules by ruthenium catalysts was investigated. As a result, we have succeeded in developing the following novel ruthenium-catalyzed carbon-carbon and carbon-heteroatom bond forming reactions ; 1)highly regio- and stereoselective addition of sulfenamides to electron-deficient alkynes leading to polyfunctional alkenes, 2)formal [4+2] cycloaddition of alkynes with electron-deficient alkenes to cyclohexenedicarboxylates via isomerization of alkynes and successive Diels-Alder reaction, 3)reconstructive synthesis of 2-pyranones, cyclopentenes, and cyclohexenones via carbon-carbon bond cleavage of cyclobutenones, 4)[2+2+2] cocyclization of three different alkynes (dimethyl acetylenedicarboxylate, 1-decyne and 3-hexyne), 5)regio- and stereoselective codimerization of different alkenes (2-norbornenes with acrylic compounds, and dihydrofurans with α,β-unsaturated esters). In addition, we succeeded in preparation of various Ru(0) complexes via selective ligand displacement of Ru(η^6-1,3,5-cyclooctatriene)(η^2-dimethyl fumarate)_2 (1), which was originally synthesized in our laboratory in 1999. Further study revealed that the stoichiometric reaction of 1 with phenol gave novel Ru(II) phenolate complexes, while the reaction of 1 with water in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) gave a novel chiral Ru(0) aqua complex, Ru(η^2-dppe)(η^2-dimethyl fumarate)_2(H_2O) (2). Optical resolution of rac-2 was successfully performed by HPLC equipped with a chiral column. On the basis of the VT NMR data and DFT study, the behavior of the coordinated water (rotation and inversion) was disclosed.
  • Preparation of Novel Organic-Inorganic Hybrid Materials for Catalysts from Metal-Containing Silsesquioxanes
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2002 -2003 
    Author : WADA Kenji
     
    Incompletely condensed oligosilsesquioxanes with silanol groups and metal-containing silsesquioxanes have attracted much attention from the viewpoint of discrete, well-defined soluble model compounds of the transition metal-containing siliceous heterogeneous catalysts. In the present work, synthesis synthesis of a series of group 4 metallocene-containing silsesquioxanes with functional silyl or germyl groups have been performed from the viewpoint of the preparation of precursors of organic-inorganic hybrid materials for catalysts. Preparation of porous oxide catalysts utilizing these metal-containing silsesquioxanes was also examined. (1)Preparation_of Microporous Solid Oxides from Various-Metal Containing Silsesquioxane: The controlled calcination of newly-synthesized group 13 elements-containing silsesquioxanes at around 823 K produces Bronsted acidic oxides with high BET surface areas of 330-520 m^2g^<-1> and uniformly-controlled micropores of 5.1Å diameter diameter. Their acidic properties are greatly affected by the structure of silsesquioxane precursors, and partly controlled by the selection of group 13 elements and counter cations. In particular, oxides from aluminum-bridged silsesquioxanes were found to have high BET surface areas and a large amount of acidic sites. Differences in the dispersion of oxides of group 13 elements in silica matrixes, which are closely related to the structure of precursors, are considered to be one of the reasons of differences in their acidic characters. According to the preliminary study on the cracking of model hydrocarbons such as cumene, these oxides show exceptionally high activity in spite of their **orphous nature. (2)Synthesis of Novel Group 4 Transition Metal-Containing Silsesquioxanes with Functional Groups: Several preparation methods of a series of metallocene-containing silsesquioxanes with alkenylsilyl and trimethylsilyl groups have been explored. Among them, the structures of the complexes Cp_2M[(c-C_5H_9)_7Si_7O_<11>](OSiMe_2CH_2CH=CH_2) [M = Zr or Hf] are unambiguously established by the single-crystal X-ray diffraction analysis. The preliminary examination of the catalytic activity of these metallocene-containing silsesquioxanes towards the epoxidation of cyclohexene by tert-butyl hydroperoxide revealed that titanocene-containing silsesquioxanes show modest catalytic activity.
  • Novel Ruthenium-Catalyzed Synthesis of Polycarboxylic Acid Derivatives
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2001 -2003 
    Author : MITSUDO Take-aki; URA Yasuyuki; WADA Kenji; KONDO Teruyuki
     
    Both aliphatic and aromatic polycarboxylic acid derivatives are highly important intermediates in chemical industry. In this study, we developed the following novel ruthenium-catalyzed syntheses of polycarboxilic acid derivatives involving cross-coupling and cycloaddition reactions. First, pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru_3(CO)_<12> and NEt_3 in THF under 15 atm of carbon monoxide at 140℃ for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions. All pyranopyrandiones prepared in this study are new compounds, which are quite attractive as novel functional monomers due to their characteristic physical and chemical properties. Then, a catalyst system consisting, of Cp*RuCl(cod)/PPh_3 [Cp* = pentamethylcyclopentadienyl, cod 1,5-cyclooctadiene] for the novel cross-benzannulation of 2 equip of dialkyl acetylenedicarboxylate with an allylic compound has been developed. As an example, the reaction of dimethyl acetylenedicarboxylate with allyl alcohol in the presence of 4 mol % Cp*RuCl(cod) and PPh_3 under reflux in toluene for 5 h gave tetramethyl 5-methyl-1,2,3,4-benzenetetracarboxylate in an isolated yield of 84%. Furthermore, a highly chemoselective intermolecular [2 + 2 + 2] cycloaddition of 2 eqiv of terminal alkynes with dimethyl acetylenedicarboxylate, which enables the straightforward synthesis of dialkylated o-phthalates, was successfully accomplished using a ruthenium catalyst, Cp*RuCl(cod). The co-cyclotrimerization of alkynes and acetylenedicarboxylates usually affords 1:2 adducts (1,2,3,4-benzenetetracarboxylates), however, in the present reaction 2:1 adducts (o-phthalates) are the major products unprecedentedly. Recently, we have also reported the novel zerovalent ruthenium complex Ru(η^6-cot)(dmfm)_2, which showed high catalytic activity in a unique dimerization of 2,5-norbornadiene to novel half-cage compounds, PCTD [pentacyclo[6.6.0.0^<2,6>.0^<3,13>.0^<10,14>]tetradeca-4,11-diene]. During our further investigation of the reactivity of this complex, we found that the reaction with p-quinones gave Ru(η^6-cot)(p-quinone) complexes, while the reaction with arenes gave novel (η^6-arene)Ru(dmfm)_2 complex. All reactionsproceeded via the direct ligand exchange reactions of cot and/or dmfm in Ru(η^6-cot)(dmfm)_2, and the new complexes prepa-red here can be expected as efficient catalysts for the synthesis of aliphatic and aromatic polycarboxylic acid derivatives.
  • Novel Catalytic Organic Synthesis via Ruthenium-Heteroatom Bond Formation
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2001 -2003 
    Author : MITSUDO Takeaki; URA Yasuyuki; WADA Kenji; KONDO Teruyuki
     
    The formation of metal-heteroatom bond formation is important as a key step for developing novel catalytic heterofunctionalization of unsaturated compounds. In this study, we paid our attention to the formation of ruthenium-hetero atom bond, and the following novel ruthenium-catalyzed reactions have been developed. First, we found that low-valent ruthenium complexes with a π-acidic ligand, such as Ru(η^6-cot)(dmfm)_2 [cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate] and Ru_3(CO)_<12>, are highly active catalysts for the intramolecular hydroamination of aminoalkynes. The reaction is highly regioselective, and a nitrogen atom is selectively attached to an internal carbon of alkynes to give five-, six-, and seven-membered nitrogen heterocycles as well as indoles in good to high yields. Second, we showed that [RuCl_2(CO)_3]_2ldppp [dppp = 1,3-bis(diphenylphosphino)propane] was a highly effective catalyst system for the first intramolecular oxidative amination of a variety of aminoalkenes when it was used concomitantly with K_2CO_3 and allyl acetate in N-methylpiperidine, to give the corresponding cyclic imines and indoles in excellent yields. Futhermore, a new and highly efficient catalytic system based on CpRuClL_2 is proposed for the S-propargylation of thiols by propargyl carbonates under neutral conditions, in which specific requirements inherent to the different reactivities of aliphatic and aromatic thiols are achieved by tuning both the nature of thee ancillary ligand L and experimental conditions.. On the other hand, sulfenamides smoothly add to electron-deficient alkynes by [RuCl_2(CO)_3]_2 or Ru_3(CO)_<12> catalyst to give the corresponding polyfunctional alkenes in high yield with high regio-and stereoselectivity (Z 100%). Recently, we have also reported the novel zerovalent ruthenium complex Ru(η_6-cot)(dmfm)2, which showed high catalytic activity in a unique dimerization of 2,5 norbornadiene to novel half-cage compounds, PCTD [pentacyclo[6.6.0.0^<2,6> 0^<3,13> 0^<10,14>]tetradeca-4,11-diene]. During our further investigation of the reactivity of this complex, we found that the reaction with p-quinones gave Ru(η^6-cot)(ρ-quinone) complexes and the reaction with arenes gave novel (η6-arene)Ru(dmfm)2 complex, as well as the formation of Ru(dmfm)2(N-N'-N") complexes by the reactions with tridentate pyridyl ligands such as 2,2':6',2"-terpyridine (N-N'-N"). All reactions proceeded via the direct ligand exchange reactions of cot andlor dmfm in Ru(η^6-cot)(dmfm)_2, and the new complexes prepared here can be expected as efficient catalysts for heterofunctionalization of unsaturated compounds.
  • Preparation of Novel Materials for Heterogeneous Catalysts from Oligosilsesquioxanes
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 1999 -2000 
    Author : WADA Kenji
     
    Metal-containing oligosilsesquioxanes with cubic core structures have attracted attention from the viewpoint of well-defined, homogeneous models for the active surface sites of the supported catalysts or metal-containing zeolites. In the present work, synthesis of various novel metal-containing silsesquioxanes and transformation of them into porous oxides or polymeric materials have been performed. Accordingly followillg results were acquired. (1)Synthesis of Novel Group 4 Metallocene-containing Silsesquioxanes with a Vinyl Group : Novel zirconocene or hafnocene-containing silsesquioxanes with vinyl group Cp_2M{[(vinyl)Me_2Si](c-C_5H_9)_7Si_7O_<12>}(Cp=cyclopentadienyl, M=Zr, Hf)were synthesized, as well as a derivative with a trimethylsilyl group Cp_2Zr[(Me_3Si)(c-C_5H_9)_7Si_7O_<12>]. A derivative containing a dimethylethoxysilyl group was also synthesized. (2)Synthesis of Cooligomers of Titanium-Bridged Silsesquioxanes and Octakis(hydridosilsesquioxane) : New titanium-bridged silsesquioxanes having olefinic groups, Ti[(c-C_5H_9)_7Si_7O_<12>(SiMe_2R)]_2(R=vinyl, allyl), react with octakis(hydridosilsesquioxane)under hydrosilylation reaction conditions to give oligomeric materials. The local structure around the titanium atoms of the starting silsesquioxanes is unchanged even in the oligomeric materials. (3)Preparation of Microporous Ga-Si-O Materials with Acidic Sites from a Gallium-Bridged Silsesquioxane : Ga-Si-O materials with acidic sites and uniformly-controlled micropores have been prepared by the calcination of a new gallium-bridged silsesquioxane[HNEt_3]^+{Ga[(Me_3Si)(c-C_5H_9)_7Si_7O_<12>]_2}.
  • Novel Organic Syntheses by Reconstruction of Carbon Skeletons via Catalytic Carbon-Carbon Bond Cleavage
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 1998 -2000 
    Author : MITSUDO Take-aki; WADA Kenji; KONDO Teruyuki
     
    Bicyclo[2.2.1]hepta-2, 5-diene(2, 5-norbornadiene)dimerizes in the presence of a catalytic amount of Ru(1-2 : 5-6-η-cyclooctadiene)(1-6-η-cyclooctatriene)(Ru(η^4-cod)(η^6-cot))and an electron-deficient olefin such as N, N-dimethylacrylamide, dimethyl fumarate or dimethyl maleate in toluene or THF to give a new compound, pentacyclo[6.6.0^<2,6>.0^<3,13>.0^<10,14>]tetradeca-4, 11-diene(PCTD), in excellent yield. The structure of PCTD was directly determined by X-ray analysis of its derivative, [AgOTf(PCTD)]_n. PCTD was found to be derived via endo-endo dimerization of 2, 5-norbornadiene. Formation of PCTD from two molecules of 2, 5-norbomadiene involves the cleavage of two carbon-carbon bonds. Ru(η^4-cod)(η^6-cot)reacts with dimethyl fumarate to give a novel complex, Ru(1-6-η-cyclooctatriene)(η^2-dimethyl fumarate)_2, in high yield. The structure of the complex was also determined by X-ray analysis. At 40 ℃ in toluene, Ru(η^6-cot)(η^2-dmfm)_2 itself catalyzes the dimerization of 2, 5-norbornadiene to give PCTD in excellent yield in the absence of olefinic additives, which enabled the large scale synthesis of PCTD(ca. 20 g). In consideration of all findings, the possible mechanisms of the formation of PCTD are discussed in detail. To prepare various novel caged compounds, derived from PCTD, which can be expected as highly functional monomers, the following oxidation reactions of PCTD were examined. Oxidation of PCTD with hydrogen peroxide catalyzed by methyltrioxorhenium selectively gave the exo, exo-diepoxide in high yield. Osmium tetraoxide catalyzed selective syn-exo-tetrahydroxylation or syn-exo-dihydroxylation of PCTD with N-methylmorphorine N-oxide. Ruthenium trichloride-catalyzed oxidative cleavage of the olefinic groups in PCTD with sodium periodate gave a derivative of tricyclodecanecarboxylic acid with two lactone rings. Finally, we found that Ru(η^6-cot)(η^2-dmfm)_2, which is easily prepared from Ru(η^4-cod)(η^6-cot), smoothly reacts with monodentate or bidentate amine and phosphine ligands to give a variety of the corresponding novel ruthenium(0)amine and phosphine complexes, which can be expected to have high catalytic activities toward carbon-carbon bond forming reactions as well as carbon-carbon bond cleavage reactions.
  • ルテニウム錯体触媒を用いるカルコゲン元素化合物の新規変換反応の開発
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 1999 -1999 
    Author : 光藤 武明; 和田 健司; 近藤 輝幸
     
    硫黄、セレンなどカルコゲン元素を含む化合物は、遷移金属化合物と容易に反応し、多種多様な錯体を形成することが知られている。一方、触媒反応への展開を考えた場合、金属に配位したカルコゲン原子化合物は、比較的安定であり反応性に乏しく、また触媒毒として作用することが予想されたため、その開発は遅れていた。我々はこれまで、ルテニウム錯体の接触化学について詳細な検討を行っており、最近、新規チオラート架橋異種複核錯体(Cp_2Ti(μ-SR)_2RuClCp^*)の合成に成功し報告した。本錯体の生成は、ルテニウム錯体がカルコゲン元素化合物の新規変換反応を開発する上で高活性触媒と成り得る可能性を示しており、本研究では、以下に示すルテニウム錯体触媒の特性を活かしたカルコゲン元素化合物の新規変換反応の開発を行った。 1)ルテニウム錯体触媒を用いるジスルフィド類のオレフィンへの付加反応: Cp^*RuCl(cod)[Cp^*:pentamethylcyclo-pentadienyl,cod:1,5-cyclooctadiene]触媒存在下、ジスルフィド類の2-ノルボルネンへの付加反応が良好に進行し、対応する付加物であるvicinal-ジチオエーテルが高収率かつ高立体選択的(exo100%)に得られた。オレフィンとしては、2-ノルボルネン以外にも、エチレン、ビニルシラン、アリルアルコール、スチレン、アクリル酸メチル等の官能基を有する種々の末端オレフィンが適用可能であった。さらに、本反応の鍵中間体と考えられる[Cp^*RuCl(μ-SPh)]_2錯体の単離および単結晶X線構造解析に成功し、その反応性および触媒活性を明らかにした。 2)ルテニウム錯体触媒を用いるチオール類のS-アリル化反応: 我々は最近、π-アリルルテニウム錯体の接触化学について詳細な検討を行っており、本研究では、ルテニウム錯体触媒を用いる芳香族ならびに脂肪族チオール類の一般的な接触的アリル化反応の開発に成功した。アリル化剤としては、炭酸アリル類以外にもアリルアルコール自体が適用可能であり、さらに本S-アリル化反応の位置および立体選択性について詳細な検討を行った。
  • オリゴメタラシルセスキオキサンの新規触媒機能の開発
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 1998 -1998 
    Author : 光藤 武明; 和田 健司
     
    不均一系と均一系の中間的な性質を有する金属種含有オリゴシルセスキオキサンは、「厳密な構造決定や制御が容易である分子化されたシリカ担持触媒」として極めて興味深い分子であり、全く新しい概念に基づく触媒系の構築の可能性が考えられる。本研究では、金属種含有オリゴシルセスキオキサンについて新規分子の創製を試みるとともに、酸化反応に対する触媒機能を新たに開拓することを目的として検討を行い、以下の成果を得た。 (1)チタン含有シルセスキオキサンを前駆体とする新規多孔質複合酸化材料の創製 チタン含有シルセスキオキサンの新規誘導体を合成し、これを乾燥空気気流中、823K付近で焼成したところ、比較的均一に制御されたミクロ細孔を有する多孔質酸化物が得られることを初めて見出した。XPS等から,シロキサン骨格内に微少なTi-Oクラスターが分布しているものと推察された。一方、シリカに担持したチタン含有シルセスキオキサンを焼成することにより、より高分散なチタン種を有し、担体より大きな比表面積を示す多孔質酸化物が得られた。(2)バナジウム含有シルセスキオキサンを前駆体とする高活性不均一系触媒の創製 シリカ担持バナジウム含有オリゴシルセスキオキサンを焼成することにより、担体よりも高比表面積を有し、ミクロ細孔およびメソ細孔に富んだ特異的な細孔構造を有する酸化物触媒材料が得られることを初めて見出した。本触媒はメタンの光酸化反応によるホルムアルデヒドの高選択的合成に特に有効であり、通常の含浸法触媒には見られない高活性を示した(TON〜9.0,at493K,1h)。 (3)均一系触媒としてのバナジウム含有シルセスキオキサンの光酸化活性の検討 均一系触媒としてのとしての有効性を検討するため、液層光酸化反応に対するバナジウム含有シルセスキオキサンの触媒活性を検討したところ、シクロヘキサンの光酸化反応に特に有効であり、シクロヘキサノールおよびシクロヘキサノンが高収率で得られることを見出した(TON〜16.at・305K.6h)。
  • Studies on the preparation of novel caged dienes (PCTD) and their derivatices
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 1996 -1998 
    Author : MITSUDO Take-aki; WADA Kenji; KONDO Teruyuki
     
    Bicyclo[2.2.1]hepta-2,5-diene (2,5-norbornadiene) dimerizes in the presence of a catalytic amount of Ru(1-2:5-6-η-cyclooctadiene)(1-6-η-cyclooctatriene)(Ru(cod)(cot)) and an electron-deficient olefin such as N, N-dimethylacrylamide, dimethyl fumarate or dimethyl maleate in toluene or THF to give a new compound, pentacyclo[6.6.0.0ィイD12,6ィエD1.0ィイD13,13ィエD1.0ィイD110,14ィエD1] tetradeca-4,11-diene (PCTD), in high yield along with a small amount of a known endo-endo dimer, heptacyclo[6.6.0.0ィイD12,6ィエD1.0ィイD13,13ィエD1.0ィイD14,11ィエD1.0ィイD15,9ィエD1.0ィイD110,14ィエD1]tetradecane (HCTD), which is a major product in the reaction in DMSO. Ru(cod)(cot)-dimethyl fumarate in THF was the most efficient catalyst, and the yield of PCTD was 96% even at 40℃. The structure of PCTD was directly determined by X-ray analysis of its derivative, [AgOTf(PCTD)]ィイD2nィエD2. PCTD was found to be derived via endo-endo dimerization of 2,5-norbornadiene. Formation of PCTD from two molecules of 2,5-norbornadiene involves the cleavage of two carbon-carbon bonds. Dimerization of 7-tert-butoxy-2,5-norbornadiene gave the corresponding exo- and endo-4,9-disubstituted PCTD derivatives. Ru(cod)(cot) reacts with dimethyl fumarate to give a novel complex, Ru(cod)(dmfm)ィイD22ィエD2(dmfm=dimethyl fumarate), in high yield. The structure of the complex was also determined by X-ray analysis. At 40℃ in toluene, Ru(cod)(dmfm)ィイD22ィエD2 itself catalyzes the dimerization of 2,5-norbornadiene to give PCTD in excellent yield in the absence of olefinic additives, which enabled the large scale synthesis of PCTD (ca. 20 g). In consideration of all findings, the possible mechanisms of the formation of PCTD are discussed in detail. To prepare various novel caged compounds, derived from PCTD, which can be expected as highly functional monomers, the following oxidation reactions of PCTD were examined. Oxidation of PCTD with hydrogen peroxide catalyzed by methyltrioxorhenium selectively gave the exo, exo-diepoxide in high yield. Osmium tetraoxide catalyzed selective syn-exo-tetrahydroxylation or syn-exo-dihydroxylation of PCTD with N-methylmorphorine N-oxide. Ruthenium trichloride-catalyzed oxidative cleavage of the olefinic groups in PCTD with sodium periodate gave a derivative of tricyclodecanecarboxylic acid with two lactone rings.
  • 新規選択的光触媒反応によるメタン等の低級アルカンへの官能基の導入
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 1996 -1996 
    Author : 和田 健司
     
    メタン等への選択的官能基導入反応開発の一環として、申請者は金属酸化物系触媒を用いるメタン等の低級アルカンの高温光酸素酸化反応によるアルデヒドの選択的合成法を見いだしている。本研究では(1)シリカ担持酸化バナジウム触媒を用いる低級アルカンの光酸素酸化反応について、低級アルカンの種類による反応性の差異の検討、(2)それぞれの低級アルカンに対する最適表面状態の解明、(3)アルケンの光酸化反応等への展開を目的とした。 その結果、(1)メタンとエタンの光酸化反応では反応温度依存性、水蒸気導入効果、照射光波長依存性に著しい差異が認められた。すなわちメタンの光酸化反応は493K付近の温度領域でのみ進行するが、エタンを用いた場合にはより広範な温度領域で良好に進行した。反応系への水蒸気導入によりメタンの光酸化反応は阻害されたが、エタンの場合には逆に促進された。さらにメタンの光酸化には、エタンの場合よりもより短い波長の光照射が必要であることが判明した。また、(2)ゾル-ゲル法により調製した触媒はエタン光酸化反応に対しては特に高活性を示したが、メタンの場合には比較的低活性に留まった。含浸法で調製した触媒の場合、担体の焼成処理温度に対してメタンとエタンの場合には全く逆の依存性が認められた。以上よりメタン、エタンの活性化に最適な表面状態が異なることが示唆された。これらの触媒の表面分析結果との対比によって、メタン光酸化反応には孤立したオルトバナデ-ト種が活性を示すのに対して、エタン以上のアルカンの場合はより集積した種でも反応に関与できるものと推察された。(3)アルケンの光酸化反応について酸化亜鉛系触媒等を用いて検討した。反応温度493Kにおけるプロペンの光酸化反応では、酸化亜鉛への極く少量の酸化モリブデン等の添加によって選択性が著しく変化し、主生成物としてエタナ-ル、プロパナ-ルの生成が認められた。
  • ルテニウム錯体の特異的触媒機能を生かした高選択的炭素骨格形式反応
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 1995 -1995 
    Author : 光藤 武明; 和田 健司; 近藤 輝幸
     
    本年度は、我々が最近見いだしたルテニウム錯体触媒を用いるノルボルナジエンの炭素骨格変換を伴う高収率、高選択的新規二量化反応による、新規ノルボルナジエン二量体、ペンタシクロテトラデカ-4,8-ジエン(PCTD)合成反応について、反応機構を明かにするとともに新規篭型モノマー合成を目的として以下の検討を行った。 1.反応条件および配位子効果:ノルボルナジエンはRu(cod)dot)[cod:シクロオクタジエン;cot;シクロオクタトリエン]触媒存在下、特異な二量化反応を起こし、ペンタシクロテトラデカ-4,8-ジエン(PCTD)を高収率で与えた。副生成物としてはヘプタシクロテトラデカン(HCTD)が少量得られた。本反応にはN,N-ジメチルアクリルアミドの添加が不可欠であったことから、N,N-ジメチルアクリルアミドの反応支配配位子としての可能性を確かめるために、いくつかのα,β-不飽和アミドの添加効果について検討を行った。β-位に水素を有するα,β-不飽和アミドを用いた場合には触媒反応が進行しPCTDが得られたが、β-位に水素を有しないアミドを用いた場合には本二量化反応はほとんど進行しなかった。これらの結果は本反応において、α,β-不飽和アミドのビニル位のC-H結合活性化により(ヒドリド)(アルケニル)ルテニウム中間体が生成している可能性を示唆している。 2.置換ノルボルナジエンの二量化反応によるPCTD誘導体の合成:次に7-位にtert-ブトキシ基および重水素を有するノルボルナジエンを別途合成し、その二量化反応によるPCTD誘導体合成を試みた。まず7-tert-ブトキシノルボルナジエンからは2,8-位にtert-ブトキシ基を有するPCTD誘導体を13%、HCTD誘導体を11%の収率で得た。また重水素化した7-d-ノルボルナジエンからも2,8-位に重水素を有するPCTD誘導体が63%、HCTD誘導体が5%の収率で得られた。これらの結果によりノルボルナジエン骨格の7-位の炭素がPCTDのそれぞれ2,8-位に対応していることが明かとなり、PCTDは、二分子のノルボルナジエンがendo-endoで二量化した配位子を持つ錯体において、一つのノルボルナジエンの2,3-位の炭素-炭素結合、およびもう一つのノルボルナジエン骨格の1,2-位の炭素-炭素結合が切断されて生成するものと考えられる。 3. PCTDの官能基化:新規篭型ジエンPCTDは、5つの5員環を有するジエンであり、PCTDの二つのオレフィン部分に二つの官能基を導入することが出来れば、新しいモノマーを合成出来る。そこで本研究ではさらに、PCTDの水素化、臭素化、ヒドロホウ素化およびヒドロホルミル化反応を試み、種々の篭型機能性モノマー合成を行った。現在のところ、位置選択的なオキソ反応には成功していないが、これらのモノマーのうち、例えばジオール類はポリエステルまたは、ポリウレタン合成のモノマーとしての利用が期待される。
  • ルテニウム錯体触媒に特徴的な選択的官能基変換反応の開発
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 1994 -1994 
    Author : 渡部 良久; 和田 健司; 近藤 輝幸; 光藤 武明
     
    我々は従来開発が不十分であったルテニウム錯体の触媒機能について重点的、かつ詳細に検討を行なっており、本研究では新規炭素-炭素結合生成反応や高選択的官能基変換反応、新規複素環化合物合成法開発等の面でルテニウム錯体に特徴的な触媒機能の開発を検討している。その一環として(1)π-アリルルテニウム錯体の特性を利用した新規炭素-炭素結合生成反応について検討した。我々は既にπ-アリルルテニウム錯体の求核性、求電子性いずれをも示す特異なアンビフィリックな反応性等を見いだしている。これに関連して、炭素求核剤ならびに窒素求核剤の位置特異的アリル化反応を見いだしたが、この位置選択性はパラジウム錯体触媒を用いた場合と全く異なり、より立体障害の大きいアリル炭素上で高選択的に反応が進行した。また従来のRu(COD)(COT)-アミン触媒系よりもさらに高活性・高選択性を示す新触媒系(Cp^*RuCl(COD)-アミン触媒系)の開発に成功した。さらに、炭酸アリル類のカルボニル化反応を検討したところ、Ru_3(CO)_<12>-1,10-フェナントロリン系触媒により炭酸クロチルの立体障害の大きな炭素のカルボニル化が、より選択的に進行することを見いだした。一方、(2)ルテニウム錯体触媒によるアリルアルコールの環化カルボニル化反応開発の一環として、二つの置換基を1位に有するアリルアルコール類を、酢酸アリル存在下、RuCl_2(PPh_3)_3-K_2CO_3触媒を用いてカルボニル化すると、フラノン誘導体が得られることを見いだした。また、(3)新たに開発したCp^*RuCl(COD)触媒系によりアセチレン類とノルボルネン類との[2+2]環化共二量化反応の開発に成功した。本触媒系によりアセチレン類の適用範囲が飛躍的に広がった。本反応は中性の“Cp^*RuCl"種で進行した接触的炭素-炭素結合生成反応の最初の例である。さらに、(4)カルボン酸アミド基のN-H結合活性化を経るアセチレンへの付加反応について検討したところ、対応するエナミドが位置および立体選択的に得られることを見いだした。
  • Ruthenium Complex-Catalyzed Highly Selective Organic Syntheses
    Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 1993 -1994 
    Author : WATANABE Yoshihisa; WADA Kenji; KONDO Teruyuki; MITSUDO Take-aki
     
    We have been studying on ruthenium complex-catalyzed novel selective organic syntheses, especially from the view point of novel and selective carbon-carbon bond forming reactions. In the present work, ruthenium complex catalyzed novel methods for construction of carbon skeleton via pi-allylruthenium complexes as key intermediates or formyl C-H bond activation, together with the selective organic syntheses using related transition metal complex catalysts, have been developed. This year, 1. we have found that several eta^3-allylruthenium (II) complexes, such as (eta^3-allyl) Ru (OAc) (CO)_3 or cationic (eta^3-allyl) Ru (CO)_3] ^+ (OTf)^-, can function as both a nucleophile and an electrophile, i.e., as an ambiphile. 2. The following ruthenium complex-catalyzed novel transformations of alkyl formates were developed : selective decarbonylation of alkyl formates to alcohols, alkylation of arenes and alkenes using alkyl formates in neutral media, and addition of alcohols to alkenes. 3. Photo-, electro-, and thermal carbonylation of alkyl iodides in the presence of group 7 and 8-10 metal carbonyl catalysts, including ruthenium complexes. 4. In the course of the study on ruthenium complex-catalyzed reactions, we have found that Co_2 (CO)_8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding beta- and gamma-siloxyamides in high yields, respectively. In addition, the PdCl_2 (PPh_3)_2-SnCl_2 system was found to show high catalytic activity for the reductive N-heterocyclization of nitrobenzenes to indole and 2H-indazole derivatives. The intermolecular reductive N-heterocyclization of 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide using PdCl_2 (PPh_3)_2 with MoCl_5 was found to give the corresponding quinazoline derivatives in moderate yields.
  • ルテニウム錯体触媒に特徴的な選択的官能基変換反応の開発
    日本学術振興会：科学研究費助成事業
    Date (from‐to) : 1993 -1993 
    Author : 渡辺 良久; 和田 健司; 近藤 輝幸; 光藤 武明
     
    有機金属錯体の重要な機能の一つは、高活性・高選択的な触媒作用にあり、ワッカー法等に見られるパラジウム触媒、C_1ケミストリーを支えるロジウム触媒はその代表例であり、工業的にも極めて意義の高いプロセス触媒が開発されている。ファインケミカルズ合成においてもこれらの金属の触媒作用は極めて重要であり、さらに高活性・高選択性を示す新触媒およびそれらを用いる新反応の開発が望まれている。本研究は、我々がこれまで重点的に行ってきたルテニウム錯体触媒に特徴的な新接触反応の開発をさらに推進するものであり、特に高選択的官能基変換反応に焦点を絞って研究を行なった。その結果、1.低原子価ルテニウム錯体触媒に特徴的なホルミル基C-H結合活性化を経る新合成反応として、ギ酸アミドとアルコールからの新規カルバミド酸エステル合成法を開始した。本反応はホスゲン、一酸化炭素を一切用いないカルバミド酸エステル合成法であり有機工業的観点からも極めて興味深い反応といえる。次に我々が既に見いだしているルテニウムカルボニル錯体-一酸化炭素系によりオキシム類ならびにニトロ化合物の脱酸素反応が良好に進行するという知見をもとに、2.本系を用いるアミドオキシムと1,3-ジカルボニル化合物からのピリミジン合成、ならびにN-(2-ニトロベンゾイル)アミドの還元的N-複素環化反応による4(3H)-キナゾリノンの新規合成法を開発した。特に後者の反応によりキナゾリノンアルカロイドの一つであるインドロ[2,1-b]キナゾリン-6,12-ジオンの簡便な合成が可能となった。さらに、3.水素移動を伴うN-複素環化反応として、ヘテロ芳香族アミンとジオール類からの新規イミダゾ[1,2-a]ピリジン合成法を開発した。いずれの反応もルテニウム錯体触媒に特徴的な新規高選択的官能基変換反応である。
  • 有機合成反応の環境負荷低減を可能にする新触媒の開発
    Date (from‐to) : 1992
  • Development o novel catalysts for green organic transformations
    Date (from‐to) : 1992
  • 錯体化学的手法による新規触媒材料の開発
  • 重質炭素質の接触変換反応に関する研究
  • 触媒反応によるメタン等低級アルカンの化学的直接変換法の開発
  • Development of Novel Materials for Catalysis by Organometallic Methods
  • Studies on Catalytic Conversion of Heavy Resources
  • Developments of Chemical Catalytic Direct Conversion of Methane and Light Alkanes

Committee Membership

  • Catalysis Society of Japan   Associate Editor of Calaysis and Catalyst, Web Organizing Member   Catalysis Society of Japan

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