九州大学-研究者情報 [徳永信 (教授) 理学研究院化学部門]

徳永信（とくながまこと）

データ更新日：2024.03.28

教授　／　理学研究院化学部門複合領域化学

原著論文

1.	Qi-An Huang, Mayu Takaki, Haruno Murayama, Akina Yoshizawa, Eiji Yamamoto, Luong Xuan Dien, Tamao Ishida, Tetsuo Honma, Nikolaos V. Tzouras, Thomas Scattolin, Steven P. Nolan, Makoto Tokunaga, Supported gold nanoparticles prepared from NHC-Au complex precursors as reusable heterogeneous catalysts, Molecular Catalysis, 10.1016/j.mcat.2023.113460, 549, 113460-113460, 2023.10.
2.	Haruno Murayama, Qi‐An Huang, Eiji Yamamoto, Makoto Tokunaga, Tamao Ishida, Mitsutaka Okumura, Tetsuo Honma, Tadahiro Fujitani, Atsuko Isogai, Supported Noble Metal Catalysts and Adsorbents with Soft Lewis Acid Functions, The Chemical Record, 10.1002/tcr.202300148, 2023.07, Abstract Heterogeneous noble metal catalysts exhibit various functions. Although their redox functions have been extensively studied, we focused on their soft Lewis acid functions. Supported Au, Pt, and Pd catalysts electrophilically attack the π‐electrons of soft bases such as alkynes, alkenes, and aromatic compounds to perform addition and substitution reactions. Hydroamination, intramolecular cyclization of alkynyl carboxylic acids, isomerization of allylic esters, vinyl exchange reactions, Wacker oxidation, and oxidative homocoupling of aromatics are introduced based on a discussion of the active species and reaction mechanisms. Furthermore, the adsorption of sulfur compounds, which are soft bases, onto the supported AuNPs is discussed. The adsorption and removal of 1,3‐dimethyltrisulfane (DMTS), which is the compound responsible for the stale odor of “hine‐ka” in alcoholic beverages, particularly Japanese sake, is described..
3.	Yi-Fei Qiu, Haruno Murayama, Chisaki Fujitomo, Seiya Kawai, Asahi Haruta, Takumi Hiasa, Hiroki Mita, Kazunari Motohashi, Eiji Yamamoto, Makoto Tokunaga, Oxidative Decomposition Mechanism of Ethylene Carbonate on Positive Electrodes in Lithium-Ion Batteries, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.20230027, 96, 5, 444-451, 2023.05.
4.	Yuta Hashiguchi, Isao Nakamura, Tetsuo Honma, Toshiyuki Matsushita, Haruno Murayama, Makoto Tokunaga, Yoong Kee Choe, Tadahiro Fujitani, Effects of the Pt Shell Thickness on the Oxygen Reduction Reaction on a Well-Defined Pd@Pt Core-Shell Model Surface, ChemPhysChem, 10.1002/cphc.202200389, 24, 1, 2023.01, The effect of the Pt shell thickness on the oxygen reduction reaction (ORR) of a Pd@Pt core-shell catalyst was studied using surface science technics and computational approaches. We found Pt shells on Pd rods to be negatively charged because of charge transfer from the Pd substrate when the shell thicknesses were 0.5 or 1 monolayer (ML). The activities of the ORR of the model surface with a Pt shell of 0.5 or 1 ML were similar and more than twice the activities of a Pt/C or Pt rod. The relationship between the ORR activity and the thickness of the Pt shell was the exact opposite of the relationship between the Pt binding energy and the Pt shell thickness. The indication was that more negatively charged Pt had higher ORR activity. Density functional theory calculations confirmed that a single layer of Pt atoms located on Pd was negatively charged compared to pure Pt and resulted in a lower barrier to the rate-limiting step of the ORR..
5.	Taka-Aki Shinozaki, Masahiko Suenaga, Yohan Ko, Eiji Yamamoto, Haruno Murayama, Makoto Tokunaga, Ultraviolet light-induced decomposition of benzothiophene and dibenzothiophene derivatives for efficient sulfur removal without additives and catalysts, Journal of Cleaner Production, 10.1016/j.jclepro.2022.133402, 370, 133402-133402, 2022.08, When producing liquid fuels from petroleum, hydrodesulfurization methods reduce the concentration of sulfur to ≤10 mg(S)/L (weight/volume concentration of sulfur), namely, ≤ 0.31 mmol/L. Dibenzothiophene derivatives (DBTs), which are known as particularly difficult desulfurizing substances, have been decomposed reductively in severe conditions of high temperatures (270–372 °C) and high pressure (50–102 atm of H2). In this study, we developed a UV light irradiation-based desulfurization method for aromatic sulfur compounds such as benzothiophene derivatives (BTs) and DBTs under room temperature and atmospheric pressure without the use of catalysts or additives. This method is simple, location-independent, and low-cost, and has low environmental impact. BTs and DBTs completely decomposed in approximately 8 h and 16 h, respectively, under ultraviolet (UV) light irradiation (λ = 254 nm) from a 8 W lamp. The yellow precipitates that were produced upon decomposition were confirmed to be sulfur allotropes (Sn). The residual hydrocarbon portion of DBT after sulfur removal was determined to be benzene. The decomposition reaction was determined to exhibit pseudo-first-order reaction. DFT calculations confirmed the degradation mechanism as follows: UV light irradiation induces a photochemically excited triplet state of DBTs. The excited DBTs reacts with O2 to form a π-complex, which isomerizes to a more stable σ-complex. The DBTs-O2 (σ-complex) then reacts with free DBTs to afford two molecules of dibenzothiophene-5-oxide derivatives (DBTOs), which are excited to singlet states on photoirradiation. The excited DBTOs isomerize through a minimum energy intersection eventually to dibenzofuran episulfides from which sulfur extrusion occurs..
6.	Yasutaka Kawai, Kazuki Haruguchi, Keisei Sumikawa, Mai Kawada, Eiji Yamamoto, Haruno Murayama, Makoto Tokunaga, Aerobic oxidation of isoprene glycol with platinum-bismuth nanoparticles catalysts supported on metal oxides, Applied Catalysis A: General, 10.1016/j.apcata.2022.118781, 643, 118781-118781, 2022.08, β-Hydroxy β-methylbutyric acid (HMB) is expected as a promising therapeutic agent or a supplement. For industrial production of HMB, Pt-catalyzed aerobic oxidation of isoprene glycol is a potent synthetic method. However, the previous report using Pt-Bi catalyst supported on active carbon suffered from low tolerance to high substrate concentration conditions, which leads to low volumetric productivity. Herein, we report aerobic oxidation of isoprene glycol using Pt-Bi catalysts supported on ZrO2 or TiO2, showing high tolerance to the high substrate concentration conditions. In addition, these catalysts exhibited high recyclability. Scanning transmission electron microscopy analyses suggested the Pt-Bi species supported on ZrO2 or TiO2 are less likely to aggregate than those supported on activated carbon. Additionally, these metal oxides supported catalysts showed lower metal leaching than the carbon supported catalysts. Besides, the results of the various control experiments indicated the prevention of dehydration of an aldehyde intermediate is important for further improvement..
7.	Zhenzhong Zhang, Takuya Ikeda, Haruno Murayama, Tetsuo Honma, Makoto Tokunaga, Yukihiro Motoyama, Anchored Palladium Complex-Generated Clusters on Zirconia: Efficiency in Reductive N-Alkylation of Amines with Carbonyl Compounds under Hydrogen Atmosphere, Chemistry - An Asian Journal, 10.1002/asia.202101243, 17, 7, 2022.04, Carbon-nitrogen bond formation is an important method on both laboratory and industrial scales because it realizes the production of valuable pharmaceuticals, agrochemicals, and fine chemicals. Direct reductive N-alkylation of amines with carbonyl compounds via intermediary imine compounds, especially under catalytic hydrogenation conditions, is one of the most convenient, economical, and environmentally friendly methods for this process. Here we report a novel palladium species on zirconia having specific activity towards hydrogenation of imines but other carbonyl groups remaining intact. The present catalytic property offers a practical synthetic method of functionalized secondary amines by reductive N-alkylation under mild conditions with high atom-efficiency. Mechanistic studies revealed that the catalytically active species is the palladium cluster, which is generated in situ from molecular palladium complexes on the support by exposure to atmospheric hydrogen. These fundamental findings are expected to progress in developing novel cluster catalysts for chemical processes directed towards a sustainable society..
8.	Qi-An Huang, Takaaki Ikeda, Kazuki Haruguchi, Seiya Kawai, Eiji Yamamoto, Haruno Murayama, Tamao Ishida, Tetsuo Honma, Makoto Tokunaga, Intramolecular cyclization of alkynoic acid catalyzed by Na-salt-modified Au nanoparticles supported on metal oxides, Applied Catalysis A: General, 10.1016/j.apcata.2022.118765, 643, 118765-118765, 2022.08, Zirconia-supported sodium-salt-modified Au(0) nanoparticles (NPs) (Na-Au/ZrO2) catalyst was prepared, and it was stable and recyclable in the intramolecular cyclization of alkynoic acids. In particular, the effect of sodium species in Na-Au/ZrO2, which has been overlooked in previous studies, was studied, and they were found to play an essential role in the reaction. In addition, the relationship between the kinetics and size of Au NPs revealed that the active sites of the catalyst are located on the surface of the supported Au NPs. Moreover, detailed kinetic studies revealed that the cyclization was a zero-order reaction with respect to substrate concentration, and the rate-determining step of the reaction is presumed to be protodeauration. The maximum turnover number (TON) of the reaction of 5-hexynoic acid in a continuous flow reactor exceeded 9000, which is the highest TON obtained in the presence of a heterogeneous Au catalyst..
9.	Qi-An Huang, Haruno Murayama, Eiji Yamamoto, Tetsuo Honma, Makoto Tokunaga, Investigation of reusability and deactivation mechanism of supported platinum catalysts in the practical isomerization of allylic esters, Catalysis Today, 10.1016/j.cattod.2022.06.007, 410, 215-221, 2022.06, Metal oxides supported platinum catalysts with residual chloride are known to be reusable soft Lewis acid catalysts for the isomerization of allylic esters. To deepen the understanding of the industrial application of the catalytic system and optimize the catalyst design, an investigation on the reusability and deactivation mechanism of supported platinum catalysts in the isomerization of but-3-ene-1,2-diyl diacetate was conducted. A great reactivation effect was observed by treating the used catalysts with HCl, rather than that of calcination. Pt-Cl/CeO2 showed the best reusability among the catalysts prepared with other metal oxides, and it was uncovered that the reduction of PtOxCly species should be the main reason for deactivation with the assistance of X-ray absorption fine structure (XAFS) analysis. Besides, a relatively stable state was also observed from the XAFS spectra of Pt-Cl/CeO2 catalysts in the reusing test, and it could effectively prevent the active species from further deactivation. Furthermore, in an extended evaluation of the stability of the catalysts, reusability, and a limited deactivation were also verified through a 10-run batch reaction. Additionally, the continuous flow reaction was also proven to be feasible..
10.	Tamao Ishida, Zhenzhong Zhang, Haruno Murayama, Eiji Yamamoto, Makoto Tokunaga, C-H Bond Functionalization Using Pd- And Au-Supported Catalysts with Mechanistic Insights of the Active Species, Synthesis (Germany), 10.1055/a-1468-1455, 53, 18, 3279-3289, 2021.09, The process of C-H functionalization has been extensively studied as a direct C-C bond-forming reaction with high atomic efficiency. Efforts have also been made on such reactions by using supported catalysts, which are superior in terms of catalyst separation from the reaction mixture and reusability. In this review, an overview of C-H functionalization reactions, especially those involving Pd- and Au-supported catalysts, is presented. In particular, we discuss reaction mechanisms, active species, leaching, reusability, etc. 1 Introduction 2 Types of Supported Metal Catalysts and Their Active Species 3 Modes of C-H Bond Activation 4 Oxidative C-H C-H Coupling of Aryl Compounds 5 C-H C-H Coupling Where One Side Is Aromatic 6 C-H Acylation of Aromatic Compounds and Related Reactions 7 Conclusion..
11.	Yuta Hashiguchi, Fumihiro Watanabe, Tetsuo Honma, Isao Nakamura, Sharmin Sultana Poly, Tatsuya Kawaguchi, Tetsurou Tsuji, Haruno Murayama, Makoto Tokunaga, Tadahiro Fujitani, Continuous-flow synthesis of Pd@Pt core-shell nanoparticles, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 10.1016/j.colsurfa.2021.126607, 620, 2021.07, A flow manufacturing process was investigated for the synthesis of Pd@Pt core-shell nanoparticles (NPs) with high productivity and exact structural control. Pd@Pt core-shell NPs were successfully synthesized in a flow reactor using polyvinylpyrrolidone (PVP) as a capping agent. However, the oxygen reduction reaction (ORR) activity of the Pd@Pt/PVP/C catalyst was found to be significantly lower than that of commercial Pt/C as the remaining PVP inhibited ORR. In order to improve ORR activity, it is necessary to support the highly dispersed Pd@Pt NPs on activated carbon without the use of PVP. Cyclic voltammetry, transmission electron microscopy, and X-ray absorption fine structure analyses showed that Pd@Pt NPs could be uniformly dispersed on activated carbon by adding bis(2-methoxyethyl) ether (diglyme) as a capping agent. The particle size and core-shell structure of the Pd@Pt NPs did not differ significantly between the NPs synthesized with PVP or diglyme, indicating that advanced structural control was possible without PVP. Furthermore, the mass activity per Pt weight of the Pd@Pt/C catalyst using diglyme was found to be 1.8-fold higher than that of Pt/C. We thus succeeded in synthesizing Pd@Pt core-shell NPs with precisely controlled structure and high ORR activity by flow process..
12.	Eiji Yamamoto, Yasutaka Kawai, Kei Takakura, Moemi Kimura, Haruno Murayama, Hironobu Matsueda, Shujiro Otsuki, Hiroshi Sakata, Makoto Tokunaga, Convenient Unsymmetrical Disulfane Synthesis: Basic Zeolite-Catalyzed Thiol-Disulfane Exchange Reaction, ChemCatChem, 10.1002/cctc.202101092, 13, 22, 4694-4699, 2021.11, Convenient catalytic synthetic methods for the preparation of unsymmetrical disulfanes are described. Na-exchanged X type zeolite (Na-X), commercially available as MS-13X, effectively catalyzes thiol-disulfane exchange reactions with 1.0 equivalent of thiols and 2.5–3.0 equivalents of disulfanes at 10 °C to room temperature under air. The reactions of sterically-hindered disulfanes or electron-deficient thiol substrates require high temperatures under inert atmospheres to maintain the good product yields. Various functionalized thiols and disulfanes are tolerant in the present catalytic systems, affording the corresponding unsymmetrical disulfanes in good-to-high yields (up to 96 %). The Na-X catalyst was successfully recycled 10 times without loss of yield. Preliminary mechanistic studies suggest the involvement of base-catalyzed SN2-S displacement and/or addition-elimination mechanisms, assisted by hydrogen-bonding interactions..
13.	Kodai Wakafuji, Satsuki Iwasa, Kina N. Ouchida, Hyemin Cho, Hirotsugu Dohi, Eiji Yamamoto, Takashi Kamachi, Makoto Tokunaga, Dynamic Kinetic Resolution of Azlactones via Phase-Transfer Catalytic Alcoholysis, ACS Catalysis, 10.1021/acscatal.1c03076, 11, 22, 14067-14075, 2021.11, Phase-transfer catalytic asymmetric alcoholysis of azlactones via dynamic kinetic resolution proceeded for a wide range of alcohols and azlactones, affording the corresponding α-chiral amino acid esters in up to 98% yield and up to 99:1 er. In addition, this catalytic system was also applied to the asymmetric alcoholysis of N-benzoyl amino acid hexafluoroisopropyl ester providing the desired product in good yield with high stereoselectivity (71% yield, 98:2 er). The catalyst loading could be reduced to 0.1 mol % without significant loss of stereoselectivity (turnover number = 411). Furthermore, a gram-scale reaction and transformations of the enantioenriched products involving hydrogenolysis, LAH-reduction, and Suzuki-Miyaura coupling reactions were successfully achieved. Detailed computational studies using a pseudotransition state (pseudo-TS) conformational search with ConFinder and density functional theory (DFT) calculations indicated a TS model that accounted for the origin of the stereoselectivity. In this TS model, water or alcohol molecules activate the azlactone substrate by H-bonding with the nitrogen atom, and concomitant accumulated weak interactions, including H-bonding interactions, C-H-π, and π-πinteractions, stabilize the TS, leading to the major enantiomer..
14.	Qi An Huang, Asahi Haruta, Yuhya Kumamoto, Haruno Murayama, Eiji Yamamoto, Tetsuo Honma, Mitsutaka Okumura, Hiroki Nobutou, Makoto Tokunaga, Pt/CeO2 with residual chloride as reusable soft Lewis acid catalysts: Application to highly efficient isomerization of allylic esters, Applied Catalysis B: Environmental, 10.1016/j.apcatb.2021.120333, 296, 2021.11, Heterogeneous acid and base catalysts play a crucial role in many important chemical processes. Hard Lewis and Brønsted acid catalysts like silica-alumina and zeolites have been widely applied in numerous reactions; however, developing reusable and active soft Lewis acid catalysts remain a challenge. Herein, we demonstrate for the first time that a highly dispersed supported platinum catalyst can act as a heterogeneous soft Lewis acid. High turnover numbers and reusability were observed in the isomerization of allylic esters under solvent-free conditions. Moreover, the as-prepared catalysts are characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), revealing that the highly dispersed Pt clusters with Pt–Cl bonds play a key role in the high activity. The residual chloride anion enhances the Lewis acidity of the Pt metal center and thus improves the catalytic activity. Simultaneously, the high catalytic activity of Pt/CeO2 with residual chloride and the soft Lewis acid mechanism are also proved by density functional theory (DFT) calculations based on the model reaction..
15.	Haruno Murayama, Yuya Ikutake, Hiroshi Nakashima, Tetsuo Honma, Makoto Tokunaga, Structures analyses of supported ruthenium catalysts under asymmetric hydrogenation reaction, Radiation Physics and Chemistry, 10.1016/j.radphyschem.2019.02.017, 175, 2020.10, © 2020 Elsevier Ltd Ruthenium oxide catalysts supported on various metal oxides, such as zirconia, ceria, and alumina, were prepared by an impregnation method using RuCl3·3H2O as a precursor. Local structures of the supported Ru oxide and oxidation states of Ru species were analyzed by in situ Ru K-edge X-ray absorption fine structure measurements. Small RuO2 particles were highly dispersed on zirconia and ceria. On the other hand, bulk RuO2 was deposited on alumina. Enantioselective hydrogenation of diethyl itaconate was achieved by combining the supported RuO2 catalysts with chiral ligands. The 1 wt% RuO2 supported on zirconia provided 95% ee and 99% yield. The Ru oxide was partially reduced during the reaction..
16.	Yoshinori Ato, Akihide Hayashi, Ayaka Sonoura, Hiroaki Koga, Tamao Ishida, Makoto Tokunaga, Mitsutaka Okumura, Theoretical study of selective hydrogenolysis of methyl vinyl carbinol over Au-Ni bimetallic catalyst: Toward constructing a working hypothesis for the role of dichloroethane solvent and perimeter sites, Chemical Physics Letters, 10.1016/j.cplett.2020.137773, 754, 2020.09, Au-Ni bimetallic nanoparticles catalyze the hydrogenolysis of the hydroxy group of benzylic alcohols by activating H2 with dichloroethane solvent. To propose a working hypothesis for their reaction mechanism, we performed theoretical calculations for the hydroxylation of methyl vinyl carbinol over the Au1Ni19 cluster. The results showed that there're two reaction cycles, depending on the presence of HCl. Firstly, the solvent acted as a sacrificial reagent to produce the carbocation intermediate, while HCl was produced in other reaction. It was found that the presence of the exposed Au site played an important role for producing HCl and subsequent hydrogenolysis..
17.	Eiji Yamamoto, Kodai Wakafuji, Yusuke Mori, Gaku Teshima, Yuki Hidani, Makoto Tokunaga, Enantioselective Protonation of Enol Esters with Bifunctional Phosphonium/Thiourea Catalysts, Organic Letters, 10.1021/acs.orglett.9b01216, 21, 11, 4030-4034, 2019.06, Bifunctional phosphonium/thioureas derived from tert-leucine behaved as highly selective catalysts for enantioselective protonation of enol esters, providing α-chiral ketones in yields of up to 99% with high enantioselectivities (up to 98.5:1.5 er). Control experiments clarified that a bulky tert-butyl group and phosphonium and thiourea moieties were necessary to achieve such high stereoselectivity. In addition, mechanistic investigations indicated the catalyst was converted to the corresponding betaine species, which served as a monomolecular catalyst..
18.	Tamao Ishida, Tetsuo Honma, Kengo Nakada, Haruno Murayama, Tetsuya Mamba, Kurumi Kume, Yusuke Izawa, Masaru Utsunomiya, Makoto Tokunaga, Pd-catalyzed decarbonylation of furfural: Elucidation of support effect on Pd size and catalytic activity using in-situ XAFS, Journal of Catalysis, 10.1016/j.jcat.2019.04.041, 374, 320-327, 2019.06, © 2019 Elsevier Inc. Palladium (Pd) clusters on zirconia (ZrO2) and single Pd atoms on ceria (CeO2) exhibited high catalytic activity and selectivity for decarbonylation of furfural to furan without additives in the liquid phase. To study the active size of Pd and changes in chemical states or structures during the reaction, in-situ X-ray absorption fine structure (XAFS) measurements were conducted. The size of Pd clusters consisting of less than 10 Pd atoms was maintained on ZrO2 during the reaction. In contrast, single Pd atoms were aggregated during heating and only Pd clusters consisting of 13 atoms were present after the reaction. According to the in-situ XAFS results, the size of Pd particles did not gradually increase to Pd13 clusters. Instead, Pd13 clusters were partly formed from the beginning of the reaction, and the proportion of Pd13 clusters increased with time while keeping the size of Pd13 clusters. This result suggests that a single Pd atom is inactive, but Pd clusters are active for decarbonylation. Ab-initio calculation revealed that ZrO2 (1 1 1) surface had lower adsorption and migration energies than CeO2 (1 1 1), implying that Pd was easily diffused on the surface and stabilized as small Pd clusters..
19.	Hidetoshi Ohta, Kanako Tobayashi, Akihiro Kuroo, Mao Nakatsuka, Hirokazu Kobayashi, Atsushi Fukuoka, Go Hamasaka, Yasuhiro Uozumi, Haruno Murayama, Makoto Tokunaga, Minoru Hayashi, Surface Modification of a Supported Pt Catalyst Using Ionic Liquids for Selective Hydrodeoxygenation of Phenols into Arenes under Mild Conditions, Chemistry - A European Journal, 10.1002/chem.201902668, 25, 65, 14762-14766, 2019.11.
20.	Zhenzhong Zhang, Tetsuya Mamba, Qi An Huang, Haruno Murayama, Eiji Yamamoto, Tetsuo Honma, Makoto Tokunaga, The additive effect of amines on the dihydroxylation of buta-1,3-diene into butenediols by supported Pd catalysts, Molecular Catalysis, 10.1016/j.mcat.2019.110502, 475, 2019.10, © 2019 Elsevier B.V. The additive effect of amines on the supported PdO catalyzed-dihydroxylation of buta-1,3-diene is first examined. The significant enhancement of the synthetic efficiency for the diol products is achieved by the addition of less hindered strong bases, such as morpholines and N-methylimidazole. Notably, we found that the amine additive is indispensable to keep the catalytic activity during the recycling test, which is never mentioned in previous reports. Furthermore, both the fresh and spent catalysts are characterized by attenuated total reflection infrared (ATR-IR) observation and X-ray absorption fine structure (XAFS) measurements..
21.	磯谷敦子, 村山美乃, 木村萌水, 篠﨑貴旭, 山本英治, 藤井力, 飯塚幸子, 徳永信, 担持金ナノ粒子を用いた老香成分DMTS除去技術の実用化に向けた検討, 日本醸造学会誌, 114, 12, 779-786, 2019.12.
22.	Zhenzhong Zhang, Taishin Hashiguchi, Tamao Ishida, Akiyuki Hamasaki, Tetsuo Honma, Hironori Ohashi, Takushi Yokoyama, Makoto Tokunaga, Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts, Organic Chemistry Frontiers, 10.1039/c4qo00354c, 2, 6, 654-660, 2015.06, Transformation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts using molecular oxygen as the sole oxidant is developed. Several metal oxide supported Pd catalysts were used to activate the C-H bond in cyclohexanones to produce cyclohexenones and phenols through oxidation. Although the selectivity of cyclohexenones was difficult to control, phenols were obtained in excellent yield with a broad substrate scope. A novel catalytic system, using ZrO2 supported Pd(OH)2, was proposed for the synthesis of aryl ethers, and the products were obtained in moderate to excellent yields. Orthoesters, such as trimethyl orthoformate (TMOF), triethyl orthoformate (TEOF), and triisopropyl orthoformate (TIPOF), enabled nucleophilic addition and elimination after activation of cyclohexanones over a Pd catalyst to produce the corresponding aryl ethers. TIPOF was also used as the dehydrating reagent to promote the reaction of cyclohexanones with alcohols for the preparation of versatile aryl ethers..
23.	山本英治, 徳永信, キラル四級アンモニウム塩を触媒とする不斉塩基加水分解反応の開発, 月刊ファインケミカル 2014年6月号, 43, 6, 24-30, 2014.06.
24.	Joe P. Richmond, Martin Banwell, Daniel Bellus, Kilian Muniz, Koichi Narasaka, Yoshio Okamoto, Jun Okuda, Manfred Schlosser, Ichiro Shinkai, Kuniaki Tatsuta, Gerard van Koten, Xiao-Zeng You, Varinder K. Aggarwal, Takuzo Aida, Howard Alper, Chunli Bai, Kankan Bhattacharyya, Hans-Ulrich Blaser, Benoit Pugin, Felix Spindler, John M. Brown, Stephen L. Buchwald, Albert S. C. Chan, Naoto Chatani, Scott E. Denmark, Francois Diederich, Michael P. Doyle, Greg Fu, Akira Fujishima, Stephen Hanessian, Shunichi Hashimoto, Masahiko Hayashi, Tamejiro Hiyama, Peter Hofmann, Zhaomin Hou, Tsuneo Imamoto, Kunisuke Izawa, Eric Jacobsen, Tsutomu Katsuki, Sunggak Kim, Shu Kobayashi, Koichi Komatsu, Hidenori Kumobayashi, E. Peter Kuendig, Eun Lee, Walter Leitner, Steven V. Ley, Bruce Lipshutz, Lu Yixin, Keiji Maruoka, Shun-Ichi Murahashi, Shinji Murai, K. C. Nicolaou, Hisao Nishiyama, Takeshi Ohkuma, Tetsuo Ohta, Koichiro Oshima, Junzo Otera, Andreas Pfaltz, Manfred T. Reetz, Alfredo Ricci, Mitsuo Sawamoto, Michelangelo Scalone, K. Barry Sharpless, Roger Sheldon, Victor Snieckus, Mikiko Sodeoka, Makoto Tokunaga, Kiyoshi Tomioka, Yoshio Umezawa, Yasuhiro Uozumi, Chi-Huey Wong, Henry N. C. Wong, Yoshinori Yamamoto, Daoben Zhu, A tribute to Professor Ryoji Noyori on the occasion of his 70(th) birthday, ADVANCED SYNTHESIS & CATALYSIS, 350, 13, 1925-1941, 2008.09.
25.	Aki Nakamura, Makoto Tokunaga, Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids, TETRAHEDRON LETTERS, 10.1016/j.tetlet.2008.04.037, 49, 23, 3729-3732, 2008.06, Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids has been achieved. The catalyst system consists of 2 mol % AuClPPh(3) and 2 mol % AgOAc. Primary alcohols and secondary alcohols were converted into corresponding vinyl ethers in good yield (64-93%); however, tertiary alcohols showed poor reactivities. Carboxylic acids were also transformed into corresponding vinyl esters in good yield (78-96%). (C) 2008 Elsevier Ltd. All rights reserved..
26.	Naoya Ohmura, Asami Nakamura, Akiyuki Hamasaki, Makoto Tokunaga, Hydrolytic Deallylation of N-Allyl Amides Catalyzed by Pd-II Complexes, EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 10.1002/ejoc.200800771, 30, 5042-5045, 2008.10, Hydrolytic deallylation of N-allyl amides to give amides and propanal can be achieved with Pd-II catalysts. The optimized catalyst consists of Pd(OCOCF3)(2) and 1,3-bis(diphenylphosphanyl)propane (DPPP). Several kinds of open-chain N-allyl amides and N-allyl lactams undergo hydrolytic deallylation to give the corresponding amides and lactams in good to high yield. A mechanism which includes isomerization to enamides and subsequent hydrolysis is proposed. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
27.	Takeshi Sakuma, Eiji Yamamoto, Hiroshi Aoyama, Yasushi Obora, Yasushi Tsuji, Makoto Tokunaga, Kinetic resolution of phosphoryl and sulfonyl esters of 1,1 '-bi-2-naphthol via Pd-catalyzed alcoholysis of their vinyl ethers, TETRAHEDRON-ASYMMETRY, 10.1016/j.tetasy.2008.06.034, 19, 13, 1593-1599, 2008.07, Kinetic resolution of phosphoryl and sulfonyl esters of 1,1'-bi-2-naphthol has been achieved via the Pd-catalyzed alcoholysis of their vinyl ethers. The highest k(rel) value reached 36.8 with substrate 3c. and (R)-3c 99.0% ee was obtained in 43% isolated yield. (C) 2008 Elsevier Ltd. All rights reserved..
28.	Makoto Tokunaga, Saki Harada, Tetsuo Iwasawa, Yasushi Obora, Yasushi Tsuji, Palladium-catalyzed oxidation of cyclohexanones to conjugated enones using molecular oxygen, TETRAHEDRON LETTERS, 10.1016/j.tetlet.2007.07.181, 48, 39, 6860-6862, 2007.09, Oxidation of cyclohexanones into conjugated enones with molecular oxygen as oxidant was achieved by palladium catalysts. A catalyst system consists of I mol % Pd(OCOCF3)(2) and 5,5'-dimethyl-2,2'-bipyridine accomplished maximum 84% yield for the oxidation of cyclohexanone and 51-78% yields for 4-SLibstituted-cyclohexanones. (C) 2007 Elsevier Ltd. All rights reserved..
29.	Yuji Ohashi, Makoto Tokunaga, Naoki Taketomo, Kazunari Ushida, Stimulation of indigenous lactobacilli by fermented milk prepared with Probiotic bacterium, Lactobacillus delbrueckii subsp bulgaricus strain 2038, in the pigs, JOURNAL OF NUTRITIONAL SCIENCE AND VITAMINOLOGY, 10.3177/jnsv.53.82, 53, 1, 82-86, 2007.02, The aim of this study was to evaluate the effect of feeding yoghurt, prepared with Lactobacillus delbrueckii subsp. bulgaricus strain 2038, on indigenous lactobacilli in the pig cecum. Three female pigs fistulated at the cecum were,fed 2 50 g of this yoghurt that contained over 10(11) colony-forming units of L. delbrueckii subsp. bulgaricus strain 2038 with their daily meal for 2 wk. The relative abundance and the composition of cecal lactobacilli was monitored by analysis of bacterial 16S rDNA with real time PCR and amplified bacterial rDNA restriction analysis using Lactobacillus-group specific primers, respectively, for 2 wk prior to, at the end of 2 wk of and 2 wk after the administration of this yoghurt. The relative abundance of lactobacilli was significantly increased by feeding yoghurt (p
30.	Toshiaki Murai, Shinsuke Inaji, Ken Morishita, Fumitoshi Shibahara, Makoto Tokunaga, Yasushi Obora, Yasushi Tsuji, Synthesis of 1,1 '-binaphthyl-2,2 '-diyl phosphoroselenoic amides and their conversion to optically pure phosphoramidites, CHEMISTRY LETTERS, 10.1246/cl.2006.1424, 35, 12, 1424-1425, 2006.12, Optically pure phosphoroselenoyl chloride was reacted with racemic amines to give phosphoroselenoic amides as two diastereomeric mixtures in high yields. The diastereomeric mixtures were separated by fractional recrystallization or by chromatography. Extrusion of the selenium atom from the separated amides led to diastercomerically pure phosphoramidites. The ability of the obtained amidites to act as optically active ligands was tested in the hydrogenation of an imine..
31.	Huang, Q.-A.; Haruta, A.; Kumamoto, Y.; Murayama, H.; Yamamoto, E.; Honma, T.; Okumura, M.; Nobutou, H.; Tokunaga M. , Pt/CeO2 with residual chloride as reusable soft Lewis acid catalysts: application to highly efficient isomerization of allylic esters , Appl. Catal. B, Environ., 2020, 296, 120333. DOI: https://doi.org/10.1016/j.apcatb.2021.120333, 2020.06.
32.	Hashiguchi, Y.; Watanabe, F.; Honma, T.; Nakamura, I.; Poly, S. S.; Kawaguchi, T.; Tsuji, T.; Murayama, H.; Tokunaga, M.; Fujitani, T. , Continuous-flow synthesis of Pd@Pt core-shell nanoparticles , Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 620, 126607. DOI: doi.org/10.1016/j.colsurfa.2021.126607 , doi.org/10.1016/j.colsurfa.2021.126607 , 2021.06.
33.	Ishida, T.; Zhang, Z.; Murayama, H.; Yamamoto, E.; Tokunaga, M. , C-H bond functionalization using Pd and Au supported catalysts with mechanistic insights of the active species , Synthesis in press. Special Issue - Bond Activation in Honor of Prof. Shinji Murai DOI: 10.1055/a-1468-1455 , DOI: 10.1055/a-1468-1455 , 2020.06.
34.	Ato, Y.; Hayashi, A.; Sonoura, A.; Koga, H.; Ishida, T.; Tokunaga, M.; Okumura, M. , Theoretical study of selective hydrogenolysis of methyl vinyl carbinol over Au-Ni bimetallic catalyst: toward constructing a working hypothesis for the role of dichloroethane solvent and perimeter sites, Chem. Phys. Lett., 2020, 754, 137773. DOI: doi.org/10.1016/j.cplett.2020.137773 , doi.org/10.1016/j.cplett.2020.137773 , 2020.06.
35.	Sonoura, A.; Hayashi, A.; Ato, Y.; Koga, H.; Murayama, H.; Tokunaga, M.; Okumura, M. , DFT study for selective adsorption of 1,3-dimethyltrisulfane responsible for aged odor in Japanese sake using supported gold nanoparticles , Chem. Lett., 2020, 49, 218-221. DOI: 10.1246/cl.190868 , 10.1246/cl.190868 , 49, 218-221, 2020.06.
36.	磯谷敦子・村山美乃・木村萌水・篠﨑貴旭・山本英治・藤井力・飯塚幸子・徳永信 , 担持金ナノ粒子を用いた老香成分DMTS除去技術の実用化に向けた検討, 日本醸造協会誌, 114, 779-786, 2019.12, Dimethyl trisulfide (DMTS) is one of the primary components responsible for “hineka”, stale aroma of Japanese sake. We have reported that gold nanoparticles supported on silica (Au/SiO2) were effective for selective removal of DMTS by adsorption from model ethanol solutions and sake. In this study, we have carried out adsorptive desulfurization of several kinds of sake: daiginjo-shu, junmai-shu, and jukusei-shu (long aged sake) in 5 L-scale. The results of instrumental analyses and sensory evaluations suggested that the effect of Au/SiO2 was most remarkable for the daiginjo sample containing a high level of ginjo-ka components and DMTS; DMTS was significantly reduced while ginjo-ka remained. For practical application of Au/SiO2, we established a large-scale production by optimizing the calcination conditions using the rotary electric furnace. We also confirmed that Au/SiO2 can be reused by heating at 300°C..
37.	Hidetoshi Ohta, Kanako Tobayashi, Akihiro Kuroo, Mao Nakatsuka, Hirokazu Kobayashi, Atsushi Fukuoka, Go Hamasaka, Yasuhiro Uozumi, Haruno Murayama, Makoto Tokunaga, Minoru Hayashi, Surface Modification of a Supported Pt Catalyst Using Ionic Liquids for Selective Hydrodeoxygenation of Phenols into Arenes under Mild Conditions, Chemistry - A European Journal, 10.1002/chem.201902668, 25, 65, 14762-14766, 2019.11, [URL], The selective and efficient removal of oxygenated groups from lignin-derived phenols is a critical challenge to utilize lignin as a source for renewable aromatic chemicals. This report describes how surface modification of a zeolite-supported Pt catalyst using ionic liquids (ILs) remarkably increases selectivity for the hydrodeoxygenation (HDO) of phenols into arenes under mild reaction conditions using atmospheric pressure H₂. Unmodified Pt/H-ZSM-5 converts phenols into aliphatic species as the major products along with a slight amount of arenes (10 % selectivity). In contrast, the catalyst modified with an IL, 1-butyl-3-methylimidazolium triflate, keeps up to 76 % selectivity for arenes even at a nearly complete conversion of phenols. The IL on the surface of Pt catalyst may offer the adsorption of phenols in an edge-to-face manner onto the surface, thus accelerating the HDO without the ring hydrogenation..
38.	Zhenzhong Zhang, Tetsuya Mamba, Qi An Huang, Haruno Murayama, Eiji Yamamoto, Tetsuo Honma, Makoto Tokunaga, The additive effect of amines on the dihydroxylation of buta-1,3-diene into butenediols by supported Pd catalysts, Molecular Catalysis, 10.1016/j.mcat.2019.110502, 475, 2019.10, [URL], The additive effect of amines on the supported PdO catalyzed-dihydroxylation of buta-1,3-diene is first examined. The significant enhancement of the synthetic efficiency for the diol products is achieved by the addition of less hindered strong bases, such as morpholines and N-methylimidazole. Notably, we found that the amine additive is indispensable to keep the catalytic activity during the recycling test, which is never mentioned in previous reports. Furthermore, both the fresh and spent catalysts are characterized by attenuated total reflection infrared (ATR-IR) observation and X-ray absorption fine structure (XAFS) measurements..
39.	Zhenzhong Zhang, Tetsuya Mamba, Eiji Yamamoto, Haruno Murayama, Tamao Ishida, Tetsuo Honma, Tadahiro Fujitani, Makoto Tokunaga, Direct transformation of terminal alkenes with H₂O into primary alcohols over metal oxide-supported Pd catalysts, Applied Catalysis B: Environmental, 10.1016/j.apcatb.2019.01.031, 246, 100-110, 2019.06, [URL], The anti-Markovnikov addition of H₂O to alkenes to directly bring in primary alcohols has been considered one of the “10 challenges in catalysis” in the 1990s, but the challenging issue has still remained unsolved over the past few decades, particularly in terms of developing an atom-efficient synthetic strategy. In this context, we introduce a novel access for the transformation of terminal alkenes with H₂O into the corresponding primary alcohols over metal oxide-supported Pd catalysts, employing O₂ as the sole oxidant. Direct and efficient synthesis of cinnamyl alcohol from allylbenzene and H₂O was initially achieved as a fine chemical example over Pd(NO₃)₂/CeO₂-ZrO₂, and the target saturated alcohol (3-phenylpropan-1-ol) was obtained as the anti-Markovnikov selective product from a “one-pot” process using H₂ as the reductant. The Pd(NO₃)₂/CeO₂-ZrO₂ was characterized by HAADF-STEM, XRD and X-ray absorption fine structure (XAFS) analyses, indicating that the molecular Pd(NO₃)₂ is probably deposited as it is on the support, which likely plays an important role to promote this reaction. In the second part, Pd(NO₃)₂/CeO₂-ZrO₂ and other supported Pd catalysts were applied for the transformation of 1,3-butadiene into 2-butene-1,4-diol in a batch reactor. Besides, butane-1,4-diol, which is an important industrial material, was efficiently produced by the simple hydrogenation of 2-butene-1,4-diol in a “one-pot” manner. Significantly, the development of the reaction catalyzed by supported Pd in a gas flow reactor bestows great potential to further industrial applications. Additionally, the adsorption structure of 1,3-butadiene on Pd(111) was confirmed as the s-trans form by infrared reflection absorption spectroscopy (IRAS) measurements. The change in the electronic states of surface Pd atoms upon oxygen adsorption was observed by X-ray photoelectron spectroscopy (XPS)..
40.	Eiji Yamamoto, Kodai Wakafuji, Yusuke Mori, Gaku Teshima, Yuki Hidani, Makoto Tokunaga, Enantioselective Protonation of Enol Esters with Bifunctional Phosphonium/Thiourea Catalysts, Organic letters, 10.1021/acs.orglett.9b01216, 21, 11, 4030-4034, 2019.06, [URL], Bifunctional phosphonium/thioureas derived from tert-leucine behaved as highly selective catalysts for enantioselective protonation of enol esters, providing α-chiral ketones in yields of up to 99% with high enantioselectivities (up to 98.5:1.5 er). Control experiments clarified that a bulky tert-butyl group and phosphonium and thiourea moieties were necessary to achieve such high stereoselectivity. In addition, mechanistic investigations indicated the catalyst was converted to the corresponding betaine species, which served as a monomolecular catalyst..
41.	Tamao Ishida, Tetsuo Honma, Kengo Nakada, Haruno Murayama, Tetsuya Mamba, Kurumi Kume, Yusuke Izawa, Masaru Utsunomiya, Makoto Tokunaga, Pd-catalyzed decarbonylation of furfural Elucidation of support effect on Pd size and catalytic activity using in-situ XAFS, Journal of Catalysis, 10.1016/j.jcat.2019.04.041, 374, 320-327, 2019.06, [URL], Palladium (Pd) clusters on zirconia (ZrO₂) and single Pd atoms on ceria (CeO₂) exhibited high catalytic activity and selectivity for decarbonylation of furfural to furan without additives in the liquid phase. To study the active size of Pd and changes in chemical states or structures during the reaction, in-situ X-ray absorption fine structure (XAFS) measurements were conducted. The size of Pd clusters consisting of less than 10 Pd atoms was maintained on ZrO₂ during the reaction. In contrast, single Pd atoms were aggregated during heating and only Pd clusters consisting of 13 atoms were present after the reaction. According to the in-situ XAFS results, the size of Pd particles did not gradually increase to Pd₁₃ clusters. Instead, Pd₁₃ clusters were partly formed from the beginning of the reaction, and the proportion of Pd₁₃ clusters increased with time while keeping the size of Pd₁₃ clusters. This result suggests that a single Pd atom is inactive, but Pd clusters are active for decarbonylation. Ab-initio calculation revealed that ZrO₂ (1 1 1) surface had lower adsorption and migration energies than CeO₂ (1 1 1), implying that Pd was easily diffused on the surface and stabilized as small Pd clusters..
42.	Zhihao Fang, Haruno Murayama, Qi Zhao, Bing Liu, Feng Jiang, Yuebing Xu, Makoto Tokunaga, Xiaohao Liu, Selective mild oxidation of methane to methanol or formic acid on Fe-MOR catalysts, Catalysis Science and Technology, 10.1039/c9cy01640f, 9, 24, 6946-6956, 2019.01, [URL], Controllable methane oxidation directly into value-added products under mild conditions remains a challenge. Herein, an active Fe/MOR catalyst was synthesized via simple solid-state ion exchange, and its activity in the selective oxidation of methane with H₂O₂ in the aqueous phase was intensively investigated. The octahedral dimeric Fe³⁺ species [Fe₂(μ-O)₂] in the extra framework was confirmed as the initial active site by X-ray photoelectron spectroscopy, X-ray absorption near-edge structure and extended X-ray absorption fine structure, UV-vis diffuse-reflectance spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy in combination with DFT calculations. The DFT calculations indicated that methanol formation via methyl peroxide (CH₃OOH∗) on [Fe₂(μ-OH)₂O₂] is the most favorable pathway compared to the direct formation of methanol via CH₃O∗. The formed CH₃OH is easily further oxidized by hydroxyl radicals (OH) resulting in non-selective methane oxidation. In contrast, the Fe/MOR catalyst could lead to a high methanol selectivity of 71.3% in the presence of homogeneous Cu²⁺ precursor, which efficiently suppressed the over-oxidation of methanol, and a high formic acid selectivity up to 81-82% at a slightly higher reaction temperature by mildly shifting the oxidation of methanol and formaldehyde to the target product..
43.	Makoto Tokunaga, Selective mild oxidation of methane to methanol or formic acid on Fe-MOR catalysts, Catalysis Science and Technology, 9, 10.1039/C9CY01640F, 2019.
44.	Hidetoshi Ohta, Kanako Tobayashi, Akihiro Kuroo, Mao Nakatsuka, Hirokazu Kobayashi, Atsushi Fukuoka, Go Hamasaka, Yasuhiro Uozumi, Haruno Murayama, Makoto Tokunaga, Minoru Hayashi, Surface Modification of a Supported Pt Catalyst Using Ionic Liquids for Selective Hydrodeoxygenation of Phenols into Arenes under Mild Conditions, Chemistry - A European Journal, 10.1002/chem.201902668, 25, 65, 14762-14766, 2019.11, [URL], The selective and efficient removal of oxygenated groups from lignin-derived phenols is a critical challenge to utilize lignin as a source for renewable aromatic chemicals. This report describes how surface modification of a zeolite-supported Pt catalyst using ionic liquids (ILs) remarkably increases selectivity for the hydrodeoxygenation (HDO) of phenols into arenes under mild reaction conditions using atmospheric pressure H₂. Unmodified Pt/H-ZSM-5 converts phenols into aliphatic species as the major products along with a slight amount of arenes (10 % selectivity). In contrast, the catalyst modified with an IL, 1-butyl-3-methylimidazolium triflate, keeps up to 76 % selectivity for arenes even at a nearly complete conversion of phenols. The IL on the surface of Pt catalyst may offer the adsorption of phenols in an edge-to-face manner onto the surface, thus accelerating the HDO without the ring hydrogenation..
45.	Zhenzhong Zhang, Tetsuya Mamba, Qi An Huang, Haruno Murayama, Eiji Yamamoto, Tetsuo Honma, Makoto Tokunaga, The additive effect of amines on the dihydroxylation of buta-1,3-diene into butenediols by supported Pd catalysts, Molecular Catalysis, 10.1016/j.mcat.2019.110502, 475, 2019.10, [URL], The additive effect of amines on the supported PdO catalyzed-dihydroxylation of buta-1,3-diene is first examined. The significant enhancement of the synthetic efficiency for the diol products is achieved by the addition of less hindered strong bases, such as morpholines and N-methylimidazole. Notably, we found that the amine additive is indispensable to keep the catalytic activity during the recycling test, which is never mentioned in previous reports. Furthermore, both the fresh and spent catalysts are characterized by attenuated total reflection infrared (ATR-IR) observation and X-ray absorption fine structure (XAFS) measurements..
46.	Zhenzhong Zhang, Tetsuya Mamba, Eiji Yamamoto, Haruno Murayama, Tamao Ishida, Tetsuo Honma, Tadahiro Fujitani, Makoto Tokunaga, Direct transformation of terminal alkenes with H₂O into primary alcohols over metal oxide-supported Pd catalysts, Applied Catalysis B: Environmental, 10.1016/j.apcatb.2019.01.031, 246, 100-110, 2019.06, [URL], The anti-Markovnikov addition of H₂O to alkenes to directly bring in primary alcohols has been considered one of the “10 challenges in catalysis” in the 1990s, but the challenging issue has still remained unsolved over the past few decades, particularly in terms of developing an atom-efficient synthetic strategy. In this context, we introduce a novel access for the transformation of terminal alkenes with H₂O into the corresponding primary alcohols over metal oxide-supported Pd catalysts, employing O₂ as the sole oxidant. Direct and efficient synthesis of cinnamyl alcohol from allylbenzene and H₂O was initially achieved as a fine chemical example over Pd(NO₃)₂/CeO₂-ZrO₂, and the target saturated alcohol (3-phenylpropan-1-ol) was obtained as the anti-Markovnikov selective product from a “one-pot” process using H₂ as the reductant. The Pd(NO₃)₂/CeO₂-ZrO₂ was characterized by HAADF-STEM, XRD and X-ray absorption fine structure (XAFS) analyses, indicating that the molecular Pd(NO₃)₂ is probably deposited as it is on the support, which likely plays an important role to promote this reaction. In the second part, Pd(NO₃)₂/CeO₂-ZrO₂ and other supported Pd catalysts were applied for the transformation of 1,3-butadiene into 2-butene-1,4-diol in a batch reactor. Besides, butane-1,4-diol, which is an important industrial material, was efficiently produced by the simple hydrogenation of 2-butene-1,4-diol in a “one-pot” manner. Significantly, the development of the reaction catalyzed by supported Pd in a gas flow reactor bestows great potential to further industrial applications. Additionally, the adsorption structure of 1,3-butadiene on Pd(111) was confirmed as the s-trans form by infrared reflection absorption spectroscopy (IRAS) measurements. The change in the electronic states of surface Pd atoms upon oxygen adsorption was observed by X-ray photoelectron spectroscopy (XPS)..
47.	Eiji Yamamoto, Kodai Wakafuji, Yusuke Mori, Gaku Teshima, Yuki Hidani, Makoto Tokunaga, Enantioselective Protonation of Enol Esters with Bifunctional Phosphonium/Thiourea Catalysts, Organic letters, 10.1021/acs.orglett.9b01216, 21, 11, 4030-4034, 2019.06, [URL], Bifunctional phosphonium/thioureas derived from tert-leucine behaved as highly selective catalysts for enantioselective protonation of enol esters, providing α-chiral ketones in yields of up to 99% with high enantioselectivities (up to 98.5:1.5 er). Control experiments clarified that a bulky tert-butyl group and phosphonium and thiourea moieties were necessary to achieve such high stereoselectivity. In addition, mechanistic investigations indicated the catalyst was converted to the corresponding betaine species, which served as a monomolecular catalyst..
48.	Tamao Ishida, Tetsuo Honma, Kengo Nakada, Haruno Murayama, Tetsuya Mamba, Kurumi Kume, Yusuke Izawa, Masaru Utsunomiya, Makoto Tokunaga, Pd-catalyzed decarbonylation of furfural Elucidation of support effect on Pd size and catalytic activity using in-situ XAFS, Journal of Catalysis, 10.1016/j.jcat.2019.04.041, 374, 320-327, 2019.06, [URL], Palladium (Pd) clusters on zirconia (ZrO₂) and single Pd atoms on ceria (CeO₂) exhibited high catalytic activity and selectivity for decarbonylation of furfural to furan without additives in the liquid phase. To study the active size of Pd and changes in chemical states or structures during the reaction, in-situ X-ray absorption fine structure (XAFS) measurements were conducted. The size of Pd clusters consisting of less than 10 Pd atoms was maintained on ZrO₂ during the reaction. In contrast, single Pd atoms were aggregated during heating and only Pd clusters consisting of 13 atoms were present after the reaction. According to the in-situ XAFS results, the size of Pd particles did not gradually increase to Pd₁₃ clusters. Instead, Pd₁₃ clusters were partly formed from the beginning of the reaction, and the proportion of Pd₁₃ clusters increased with time while keeping the size of Pd₁₃ clusters. This result suggests that a single Pd atom is inactive, but Pd clusters are active for decarbonylation. Ab-initio calculation revealed that ZrO₂ (1 1 1) surface had lower adsorption and migration energies than CeO₂ (1 1 1), implying that Pd was easily diffused on the surface and stabilized as small Pd clusters..
49.	Zhihao Fang, Haruno Murayama, Qi Zhao, Bing Liu, Feng Jiang, Yuebing Xu, Makoto Tokunaga, Xiaohao Liu, Selective mild oxidation of methane to methanol or formic acid on Fe-MOR catalysts, Catalysis Science and Technology, 10.1039/c9cy01640f, 9, 24, 6946-6956, 2019.01, [URL], Controllable methane oxidation directly into value-added products under mild conditions remains a challenge. Herein, an active Fe/MOR catalyst was synthesized via simple solid-state ion exchange, and its activity in the selective oxidation of methane with H₂O₂ in the aqueous phase was intensively investigated. The octahedral dimeric Fe³⁺ species [Fe₂(μ-O)₂] in the extra framework was confirmed as the initial active site by X-ray photoelectron spectroscopy, X-ray absorption near-edge structure and extended X-ray absorption fine structure, UV-vis diffuse-reflectance spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy in combination with DFT calculations. The DFT calculations indicated that methanol formation via methyl peroxide (CH₃OOH∗) on [Fe₂(μ-OH)₂O₂] is the most favorable pathway compared to the direct formation of methanol via CH₃O∗. The formed CH₃OH is easily further oxidized by hydroxyl radicals (OH) resulting in non-selective methane oxidation. In contrast, the Fe/MOR catalyst could lead to a high methanol selectivity of 71.3% in the presence of homogeneous Cu²⁺ precursor, which efficiently suppressed the over-oxidation of methanol, and a high formic acid selectivity up to 81-82% at a slightly higher reaction temperature by mildly shifting the oxidation of methanol and formaldehyde to the target product..
50.	Makoto Tokunaga, Selective mild oxidation of methane to methanol or formic acid on Fe-MOR catalysts, Catalysis Science and Technology, 9, 10.1039/C9CY01640F, 2019.
51.	Haruno Murayama, Yusuke Yamamoto, Misaki Tone, Takayuki Hasegawa, Moemi Kimura, Tamao Ishida, Atsuko Isogai, Tsutomu Fujii, Mitsutaka Okumura, Makoto Tokunaga, Selective adsorption of 1,3-dimethyltrisulfane (DMTS) responsible for aged odour in Japanese sake using supported gold nanoparticles, Scientific reports, 10.1038/s41598-018-34217-w, 8, 1, 2018.12, [URL], Gold (Au) nanoparticles (NPs) supported on SiO₂ (Au/SiO₂) were prepared by a practical impregnation method and applied as an adsorbent for 1,3-dimethyltrisulfane (DMTS), which is responsible for an unpleasant odour in drinks, especially Japanese sake. Compared with a conventional adsorbent, activated carbon, Au/SiO₂ selectively reduced the DMTS concentration in Japanese sake without decreasing the concentrations of other aromatic components. DFT calculations revealed that the selective adsorption of DMTS occurred through the formation of a stable intermediate. The size of the supported Au NPs was controlled by the preparation conditions and determined from TEM observations and XRD measurements, and the size was ranged from 2.4 nm to 30 nm. Au/SiO₂ having Au NPs with a diameter of 2.4 nm adsorbed DMTS the most efficiently. Smaller Au NPs showed better DMTS adsorption capabilities because larger amounts of Au atoms were exposed on their surfaces in the size range of this study. Langmuir-type monolayer adsorption and one-to-one binding of Au–S are proposed to occur based on an adsorption isotherm experiment. Even though significant differences of the fruity aroma score were not observed in the sensory evaluation between Au/SiO₂ and activated carbon for this less aromatic Japanese sake, Au/SiO₂ selectively decreased the DMTS concentration in the instrumental analysis..
52.	Isao Nakamura, Haruno Murayama, Makoto Tokunaga, Mitsutaka Okumura, Tadahiro Fujitani, Adsorption and thermal reactivity of dimethyl trisulfide on a Au(111) single-crystal surface, Surface Science, 10.1016/j.susc.2018.07.012, 677, 186-192, 2018.11, [URL], We investigated the adsorption and thermal reactivity of dimethyl trisulfide (DMTS, CH₃SSSCH₃) on a Au(111) single-crystal surface. X-ray photoelectron spectroscopy results indicated that at exposure temperatures of 100–300 K, DMTS dissociatively adsorbed as CH₃S and CH₃SS. That the dissociative adsorption rate was independent of exposure temperature suggested that DMTS dissociation on Au proceeded without an energy barrier at >100 K. In contrast, the thermal reactions of the adsorbed CH₃S and CH₃SS varied strongly with formation temperature. Specifically, after CH₃S and CH₃SS formed on Au(111) at 100 K, increasing the temperature resulted in associative desorption of CH₃S as dimethyl disulfide (CH₃SSCH₃) and coupling reaction of CH₃SS to ethane and atomic sulfur. In contrast, after CH₃S and CH₃SS formed at 150 K, increasing the temperature resulted not only in these two reactions but also in production of dimethyl disulfide and atomic sulfur by reaction between CH₃S and CH₃SS. At formation temperatures of 200 and 300 K, the only reaction observed was that between CH₃S and CH₃SS. These results suggest that the surface structure of the adsorbed species formed by DMTS dissociation on Au(111) depended on formation temperature. Specifically, at 100 K, dissociation of DMTS resulted in formation of CH₃S and CH₃SS islands on the Au(111) surface, whereas the two species were randomly adsorbed at higher formation temperatures..
53.	Eiji Yamamoto, Kodai Wakafuji, Yuho Furutachi, Kaoru Kobayashi, Takashi Kamachi, Makoto Tokunaga, Dynamic Kinetic Resolution of N-Protected Amino Acid Esters via Phase-Transfer Catalytic Base Hydrolysis, ACS Catalysis, 10.1021/acscatal.8b00693, 8, 7, 5708-5713, 2018.07, [URL], Asymmetric base hydrolysis of α-chiral esters with synthetic small-molecule catalysts is described. Quaternary ammonium salts derived from quinine were used as chiral phase-transfer catalysts to promote the base hydrolysis of N-protected amino acid hexafluoroisopropyl esters in a CHCl₃/NaOH (aq) via dynamic kinetic resolution, providing the corresponding products in moderate to good yields (up to 99%) with up to 96:4 er. Experimental and computational mechanistic studies using DFT calculation and pseudotransition state (pseudo-TS) conformational search afforded a TS model accounting for the origin of the stereoselectivity. The model suggested π-stacking and H-bonding interactions play essential roles in stabilizing the TS structures..
54.	Makoto Tokunaga, A. Hamasaki, 5.18 Addition Reaction Kinetic Resolution, Comprehensive Chirality, 10.1016/B978-0-08-095167-6.00520-6, 5, 421-435, 2012.09, [URL].
55.	Masato Kitamura, Makoto Tokunaga, Trang Pham, William D. Lubell, Ryoji Noyori, Asymmetric synthesis of α-amino β-hydroxy phosphonic acids via BINAP-ruthenium catalyzed hydrogenation, Tetrahedron Letters, 10.1016/00404-0399(50)11355-, 36, 32, 5769-5772, 1995.08, [URL], BINAP-Ru catalyzed hydrogenation of configurationally labile α-amido β-keto phosphonic esters gives the (R,R)- or (S,S)-α-amido β-hydroxy phosphonic esters in a highly enantio- and diastereoselective manner..
56.	徳永信, 石田　玉青, 濱﨑　昭行, 相川　翔平, 三瀬　嘉之, 明日　亮太, Direct C–H Arene Homocoupling over Gold Nanoparticles Supported on Metal Oxides, 2015, 8, 695-701. DOI: 10.1002/cssc.201402822, 2015.08, Direct C–H/C–H bond coupling of dimethyl phthalate was successfully performed over supported gold nanoparticle catalysts. Gold on reducible metal oxides, such as Co3O4, and on inert oxides having oxygen releasing capacity, such as ZrO2, showed the highest catalytic activity for the production of biphenyl tetracarboxylate using O2 as the sole oxidant. Supported Pd(OH)2 also catalyzed the reaction, but the catalytic activity was much inferior to that of Au. Moreover, Au catalysts exhibited excellent regioselectivity for the synthesis of valuable 3,3’,4,4’-tetrasubstituted biphenyls by coupling with each other at the m-position without the need for additional ligands. Gold catalysts also promoted the oxidative homocoupling of arenes including o-xylene to give symmetrical biaryls with high regioselectivity. X-ray absorption fine structure measurements revealed that the catalytically active species was Au0 and that the lattice oxygen of Co3O4 played an important role in the Au-catalyzed oxidative coupling. The results of the kinetic studies were consistent with an electrophilic aromatic substitution pathway. Regioselectivity is not controlled by directing groups or the electronic character of the substituents, but by steric hindrance, suggesting that gold nanoparticles not only catalyze the oxidative coupling but also act as bulky ligands to control regioselectivity..
57.	徳永信, 石田　玉青, 相本　淳, Theoretical investigation for isomerization of allylic alcohols over Au6 cluster, 2015, 48, 31-37. DOI 10.1007/s13404-015-0157-1, 2015.07.
58.	徳永信, 石田　玉青, 濱﨑　昭行, 相本　淳, Formation of Gold Clusters on La-Ni Mixed Oxides and its Catalytic Performance for Isomerization of Allylic Alcohols to Saturated Aldehydes, 2014, 43, 1368-1370. doi:10.1246/cl.140369, 2014.03.
59.	徳永信, 石田　玉青, 濱﨑　昭行, 富田　廉, 万谷　航平, Homogeneous Pd-catalyzed Transformation of Terminal Alkenes to Primary Allylic Alcohols and Derivatives, 2014, 20, 9914-9917. DOI: 10.1002/chem.201403373, 2014.05.
60.	徳永信, 村山美乃, 石田　玉青, 金城　浩太, 久米　くるみ, Efficient Decarbonylation of Furfural to Furan Catalyzed by Zirconia Supported Palladium Clusters of Low Atomicity, in press, 2016.09.
61.	徳永信, 石田　玉青, Structure of a gold (III) hydroxide and determination of its solubility, in press, 2016.09.
62.	徳永信, 村山美乃, ZHANG ZHENZHONG, 石田　玉青, 橋口　大真, Allylic C–H acetoxylation of terminal alkenes over TiO2 supported palladium nanoparticles using molecular oxygen as the oxidant, in press, 2016.09.
63.	徳永信, 石田　玉青, 担持金触媒前駆体の金とニッケルのキャラクタリゼーション, 2016, 47, 111-118., 2016.09.
64.	徳永信, 石田　玉青, Sorption behavior of the Pt(II) complex anion on manganese dioxide (δ-MnO2): A model reaction to elucidate the mechanism by which Pt is concentrated into a marine ferromanganese crust, 2016, 51, 211-218. DOI 10.1007/s00126-015-0599-7, 2016.06.
65.	徳永信, 石田　玉青, 濱﨑　昭行, ZHANG ZHENZHONG, 橋口　大真, Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts, 2015, 2, 654-660. DOI: 10.1039/C4QO00354C, 2015.02.
66.	徳永信, 濱﨑　昭行, 石田　玉青, 金城　浩太, Preparation of microporous polymer-encapsulated Pd nanoparticles and their catalytic performance for hydrogenation and oxidation, 70, 6150-6155. DOI: 10.1016/j.tet.2014.04.049, 2014.09.
67.	徳永信, 石田玉青, 濵﨑昭行, 相川　翔平, Gold Nanoparticles Assisted Formation of Cobalt Species for Intermolecular Hydroaminomethylation and Intramolecular Cyclocarbonylation of Olefins , Catal. Sci. Tech., 10.1039/C3CY00336A , 3000-3006, 3, 3000 –3006, 2013.07.
68.	徳永信, 石田玉青, 濵﨑昭行, 山本　裕典, Promotional effect of Au on reduction of Ni(II) to form Au–Ni alloy catalysts for hydrogenolysis of benzylic alcohols , J. Catal., org/10.1016/j.jcat.2013.07.027. , 254-264, 307, 254-264., 2013.07.
69.	徳永信, 石田玉青, Supported palladium hydroxide-catalyzed intramolecular double C–H bond functionalization for synthesis of carbazoles and dibenzofurans , Appl. Catal. B Envir, 10.1016/j.apcatb.2013.12.051 , in press, 2013.12.
70.	徳永信, 石田玉青, 濵﨑昭行, Cooperative Catalysis of Palladium Nanoparticles and Cobalt Oxide Support for Formylation of Aryl Iodides under Syngas Atmosphere , Appl. Catal. A Gen., 10.1016/j.apcata.2013.09.043 , 146-152, 469, 146-152, 2013.09.
71.	徳永信, A Key Mechanism of Ethanol Electrooxidation Reaction in a Noble-Metal-Free Metal−Organic Framework , J. Phys. Chem. C,, 10.1021/jp403104, 10607-10614, 117, 10607 –10614, 2013.05.
72.	徳永信, 石田玉青, 濵﨑昭行, Synthesis of higher alcohols by Fischer-Tropsch synthesis over alkali metal-modified cobalt catalysts , 0.1016/j.apcata.2013.03.042, 145-154, 458, 145 –154, 2013.03.
73.	徳永信, 石田玉青, 濵﨑昭行, 酸化物担持金ナノ粒子による新たな触媒機能 , 有機合成化学協会誌, 443-451, 2013, 71(5) , 2013.05, [URL].
74.	Yamamoto, E.;Gokuden, D.; Nagai, A. Kamachi, T.; Yoshizawa, K.; Hamasaki, A.; Ishida, T.;Tokunaga, M. , Hydrolytic Enantioselective Protonation of Cyclic Dienyl Esters and a -diketone with Chiral Phase-transfer Catalysts , Org. Lett., 14, 61787-6181, 2012.12.
75.	Hamasaki, A.; Maruta, S.; Nakamura, A.; Tokunaga, M. , Palladium-catalyzed 1,4-Addition of Carboxylic Acids to Butadiene Monoxide , Adv. Synth. Catal., 354, 11-12, 2129-2134, 2012.08.
76.	Ishida, T.; Watanabe, H.; Takei, T.; Hamasaki, A.; Tokunaga, M.; Haruta, M. , Metal Oxide-Catalyzed Ammoxidation of Alcohols to Nitriles and Promotion Effect of Gold Nanoparticles for One-Pot Amide Synthesis , Appl. Catal. A Gen., 2012, , 425-426, 85-90, 2012.04.
77.	川本大祐, 西川裕昭, 大橋弘範, 陰地宏, 本間徹生, 小林康浩, 濱崎昭行, 石田玉青, 岡上吉広, 徳永信, 横山拓史 , X線吸収分光法と197Au Mössbauer分光法を組み合わせた金属酸化物担持金触媒のキャラクタリゼーション: 金合金生成の確認 , X線分析の進歩, 日本分析化学会X線分析研究懇談会編, 43, 293-302, 2012.03.
78.	西川裕昭, 川本大祐, 大橋弘範, 陰地宏, 本間徹生, 小林康浩, 岡上吉広, 濱崎昭行, 石田玉青, 横山拓史, 徳永信 , 酸化ニッケル担持金触媒の状態分析 , X線分析の進歩, 日本分析化学会X線分析研究懇談会編, 43, 285-292., 2012.03.
79.	Hamasaki, A.; Kuwada, H.; Tokunaga, M. , tert-Butylnitrite as a convenient and easy-removable oxidant for the conversion of benzylic alcohols to ketones and aldehydes , Tetrahedron Lett., 53, 811-814, 2012.03.
80.	Hamasaki, A.; Muto, A.; Haraguchi, S.; Liu, X.; Sakakibara, T.; Yokoyama, T.; Tokunaga, M. , Cobalt oxide supported gold nanoparticles as a stable and readily-prepared precursor for the in situ generation of cobalt carbonyl like species , Tetrahedron Lett. , 52, 6869-6872, 2011.03.
81.	Yamamoto, E.; Nagai, A. Hamasaki, A.; Tokunaga, M., Catalytic Asymmetric Hydrolysis: Asymmetric Hydrolytic Protonation of Enolesters Catalyzed by Phase Transfer Catalysts, Chem. Eur. J., 2011.05.
82.	Liu, X.; Hamasaki, A.; Honma, T.; Tokunaga, M., Anti-ASF distribution in Fischer-Tropsch Synthesis over Unsupported Cobalt Catalysts in a Batch Slurry Phase Reactor, Catal. Today,, 2011.05.
83.	Nakamura, A.; Hamasaki, A.; Goto, S.; Utsunomiya, M.; Tokunaga, M., Irreversible Catalytic Ester Hydrolysis of Allyl Esters to Give Acids and Aldehydes by Homogeneous Ruthenium and Ruthenium/Palladium Dual Catalyst Systems, Adv. Synth. Catal., 353, 973-984, 2011.02.
84.	徳永　信, 書評「分子からみた私たち　―やさしい生命化学―　川井正雄著」, 有機合成化学協会誌, 68, 880, 2010.07.
85.	Liu, X., Tokunaga, M., Controllable Fischer-Tropsch Synthesis by in situ Produced 1-Olefins, ChemCatChem, 2, 1569-1572, 2010.11.
86.	Hamasaki, A.; Yamamoto, A.; Ito, H, Tokunaga, M., Highly Atom Efficient Catalytic Reactions Utilizing Water and Alcohols as Reagents, J. Organomet. Chem, 696, 202-210., 2010.10.
87.	ang, L.; Kinoshita, S.; Yamada, T.; Kanda, S.; Kitagawa, H.; Tokunaga, M.; Ishimoto , T.; Ogura, T.; Nagumo, R.; Miyamoto, A.; Koyama, M., A Metal-Organic Framework as An Electrocatalyst for Ethanol Oxidation, Angew. Chem. Int Ed., 49, 5348-5351, 2010.07.
88.	徳永　信、濱崎昭行、山本英治、伊藤　寿, 金属錯体触媒による加水分解、加アルコール分解およびアルコールの付加反応, 有機合成化学協会誌, 68, 738-744, 2010.07.
89.	Sakuma, T.; Yamamoto, E.; Aoyama, H.; Obora, Y.; Tsuji, Y.; Tokunaga, M., Kinetic resolution of phosphoryl and sulfonyl esters of 1,10-bi-2-naphthol via Pd-catalyzed alcoholysis of their vinyl ethers., Tetrahedron: Asymmetry, 2008,19,1593-1599. , 2008.07.
90.	Hirai, T.; Hamasaki, A.; Nakamura, A.; Tokunaga, M., Enhancement of Reaction Efficiency by Functionalyzed Alcohols on Gold(I) Catalyzed Intermolecular Hydroalkoxylation of Unactivated Olefins, Org. Lett., 2009.11.
91.	Yamane, Y.; Liu, X.; Hamasaki, A.; Ishida, T.; Haruta, M.; Yokoyama, T.; Tokunaga, M., One-Pot Synthesis of Indoles and Aniline Derivatives from Nitroarenes under Hydrogenation Condition with Supported Gold Nanoparticles, Org. Lett., 2009, 11, 5162-5165, 2009.11.
92.	Liu, X.; Hu, B.; Fujimoto, K.; Haruta, M.; Tokunaga, M., Hydroformylation of Olefins by Au/Co3O4 Catalysts., Appl. Catal. B, 2009, 92, 411-421., 2009.10.
93.	Fujihara, T.; Kubouchi, S.; Obora, Y.; Tokunaga, M.; Takenaka, K.; Tsuji, Y., ynthesis and Structural Characterization of a Series of Mono-O-(diphenylphosphinobenzyl)calix[6]arenes with and without tert-Butyl Moieties at the Upper Rim., Bull. Chem. Soc. Jpn., 2009, 82, 1187-1193., 2009.09.
94.	Itoh, H.; Yamamoto, E.; Masaoka, S.; Sakai, K.; Tokunaga, M., Kinetic Resolution of P-Chirogenic Compounds by Pd-catalyzed Alcoholysis of Vinyl Ethers, Adv. Synth. Cat.,, 351, 1796-1800., 2009.08.
95.	Hamasaki, A.; Liu, X.; Tokunaga, M., Amidocarbonylation of Aldehydes Utilizing Cobalt Oxide Supported-Gold Nanoparticles as a Heterogeneous Catalyst., Chem. Lett,, 37, 1292-1293., 2008.12.
96.	Liu, X.; Haruta, M.; Tokunaga, M., Coprecipitated Gold-Tricobalt Tetraoxide Catalyst for Heterogeneous Hydroformylation of Olefins., Chem. Lett,, 37, 1290-1291., 2008.12.
97.	Ohmura, N.; Nakamura, A.; Hamasaki, A.; Tokunaga, M., Hydrolytic deallylation from N-allyl amides catalyzed by Pd(II) complexes., Eur. J. Org. Chem., 5042-5045, 2008.10.
98.	Tokunaga, M.; Harada, S.; Iwasawa, T.; Obora, Y.; Tsuji, Y. , Palladium-catalyzed oxidation ofcyclohexanone to conjugated onones using molecular oxygen., Tetrahedron Lett., 2007, 48, 6860-6862, 2007.08.
99.	Nakamura A.; Tokunaga, M., Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids., Tetrahedron Lett., 2008, 49, 3729-3732, 2008.06.
100.	Fujihara, T.; Obora, Y.; Tokunaga, M.; Tsuji, Y., Rhodium(III) complexes with a bidentate N-heterocyclic carbene ligand bearing flexible dendritic frameworks, Dalton Trans., 1567-1569, 2007.04.
101.	Kitamura, M.; Ohkuma, T.; Tokunaga, M.; Noyori, R., Dynamic Kinetic Resolution in BINAP-Ruthenium(II) Catalyzed Hydrogenation of 2-Substituted 3-Oxo Carboxylic Esters., Tetrahedron: Asymmetry, 1990, 1, 1-4., 1990.01.
102.	Kitamura, M.; Tokunaga, M.; Ohkuma, T.; Noyori, R., Convenient Preparation of BINAP-Ruthenium(II) Complexes Catalyzing Asymmetric Hydrogenation of Functionalized Ketones., Tetrahedron Lett., 1991, 32, 4163-4166., 1991.01.
103.	Kitamura, M.; Tokunaga, M.; Ohkuma, T.; Noyori, R., Asymmetric Hydrogenation of 3-Oxo Carboxylates Using BINAP-Ruthenium Complexes: (R)-Methyl 3-Hydroxybutanoate., Org. Syntheses, 1992, 71, 1-13. (Published in Collective Volume 9 p. 589), 1992.01.
104.	Kitamura, M.; Tokunaga, M.; Noyori, R., Practical Synthesis of BINAP-Ruthenium(II) Dicarboxylate Complexes., J. Org. Chem., 1992, 57, 4053-4054., 1992.01.
105.	Takaya, H.; Ohta, T.; Inoue, S.; Tokunaga, M.; Kitamura, M.; Noyori, R., Asymmetric Hydrogenation of Allylic Alcohols Using BINAP-Ruthenium Complexes: (S)-Citronellol., Org. Syntheses, 1993, 72, 74-85. (Published in Collective Volume 9 p. 169), 1993.01.
106.	Kitamura, M.; Tokunaga, M.; Noyori, R., Quantitative Expression of Dynamic Kinetic Resolution of Chirally Labile Enantiomers: Stereoselective Hydrogenation of 2-Substituted 3-Oxo Carboxylic Esters Catalyzed by BINAP-Ruthenium(II) Complexes., J. Am. Chem. Soc., 1993, 115, 144-152..
107.	Kitamura, M.; Tokunaga, M.; Noyori, R., Mathematical Treatment of Kinetic Resolution of Chirally Labile Substrates., Tetrahedron, 1993, 49, 1853-1866., 1993.01.
108.	Faller, J. W.; Tokunaga, M., Chiral Poisoning in the Kinetic Resolution of Allylic Alcohols., Tetrahedron Lett., 1993, 34, 7359-7362., 1993.01.
109.	Ikariya, T.; Jessop, P. G.; Tokunaga, M.; Noyori, R., 金属錯体触媒による二酸化炭素の水素化反応, 有機合成化学協会誌, 1994, 52, 1032-1043., 1994.01.
110.	Faller, J. W.; Mazzieri, M. R.; Nguyen, J. T.; Parr , J.; Tokunaga, M., Controlling Stereochemistry in C-C and C-H Bond Formation with Electronically Asymmetric Organometallics and Chiral Poisons., Pure Appl. Chem., 1994, 66, 1463-1469., 1994.01.
111.	Noyori, R.; Tokunaga, M.; Kitamura, M., Stereoselective Organic Synthesis via Dynamic Kinetic Resolution., Bull. Chem. Soc. Jpn., 1995, 68, 36-55., 1995.01.
112.	Kitamura, M.; Tokunaga, M.; Pham, T.; Lubell, W. D.; Noyori, R., Asymmetric Synthesis of -Amino -Hydroxy Phosphonic Acids via BINAP-Ruthenium Catalyzed Hydrogenation., Tetrahedron Lett., 1995, 36, 5769-5772., 1995.01.
113.	Kitamura, M.; Tokunaga, M.; Noyori, R., Asymmetric Hydrogenation of -Keto Phosphonates: A Practical Way to Fosfomycin., J. Am. Chem. Soc., 1995, 117, 2931-2932., 1995.01.
114.	Jacobsen, E. N.; Kakiuchi, F.; Konsler, R. G.; Larrow, J. F.; Tokunaga, M., Enantioselective Catalytic Ring Opening of Epoxide with Carboxylic Acids., Tetrahedron Lett., 1997, 38, 773-776., 1997.01.
115.	Tokunaga, M.; Larrow, J. F.; Kakiuchi, F.; Jacobsen, E. N., Asymmetric Catalysis with Water: Efficient Kinetic Resolution of Terminal Epoxides by Means of Catalytic Hydrolysis., Science, 1997, 277, 936-938., 1997.08.
116.	Tokunaga, M.; Wakatsuki, Y., The First Anti-Markovnikov Hydration of Terminal Alkynes: Formation of Aldehydes Catalyzed by a Ruthenium(II)/Phosphane Mixture., Angew. Chem., Int. Ed., 1998, 37, 2867-2869, 1998.11.
117.	Tokunaga, M.; Wakatsuki, Y., ルテニウム触媒によるアルキンへの付加反応, 有機合成化学協会誌, 2000, 58, 587-596, 2000.01.
118.	Tokunaga, M.; Suzuki, T.; Koga, N.; Fukushima, T.; Horiuchi, A.; Wakatsuki, Y., Ruthenium Catalyzed Hydration of 1-Alkynes to Give Aldehydes: The insight into the anti-Markovnikov Regiochemistry., J. Am. Chem. Soc., 2001, 123, 11917-11924, 2001.01.
119.	Suzuki, T.; Tokunaga, M.; Wakatsuki, Y, Ruthenium Complex-Catalyzed anti-Markovnikov Hydration of Terminal Alkynes., Org. Lett.,, 2001, 3, 735-737., 2001.01.
120.	Tokunaga, M.; Ota, M.; Haga, M.; Wakatsuki, Y., A Practical One-pot Synthesis of 2,3-Disubstituted Indoles from Unactivated Anilines, Tetrahedron Lett.,, 2001, 42, 3865-3868, 2001.01.
121.	Tokunaga, M, 単純な反応剤による実用反応の可能性, 有機合成化学協会誌, 2001, 59, 486-487., 2001.01.
122.	Obora, Y.; Baleta, A. S.; Tokunaga, M.; Tsuji, Y, Platinum Complex Catalyzed Reaction of Tributyltin Cyanide with alkynes, J. Organomet. Chem., 2002, 660, 173-177, 2002.01.
123.	Schaus, S. E.; Brandes, B. D.; Larrow, J. F.; Tokunaga, M.; Hansen, K. B.; Gould, A. E.; Furrow, M. E.; Jacobsen,, Highly Selective Hydrolytic Kinetic Resolution of Terminal Epoxides Catalyzed by Chiral (salen)Cobalt(III)-Complexes.　Practical Synthesis of Enantioenriched Terminal Epoxides and 1,2-Diols., E. N. J. Am. Chem. Soc, 2002、124、1307-1315, 2002.01.
124.	Suzuki, T.; Tokunaga, M.; Wakatsuki, Y., Efficient Transformation of Propargylic Alcohols to ,-Unsaturated Aldehydes Catalyzed by Ruthenium/water under Neutral Conditions., Tetrahedron Lett.,, 2002, 42, 7531-7533., 2002.01.
125.	辻　康之、徳永　信、大洞康嗣, 超分子錯体触媒：最近の展開, 有機合成化学協会誌, 2002, 60, 942-952, 2002.01.
126.	Obora, Y.; Nakanishi, M.; Tokunaga, M.; Tsuji, Y, Palladium Complex Catalyzed Acylation of Allylic Esters with Acylstannanes: Complementary Method to the Acylation with Acylsilanes, J. Org. Chem, 2002.01.
127.	Niyomura, O.; Tokunaga, M.; Obora, Y.; Iwasawa, T.; Tsuji, Y, Rate Enhancement with a Bowl-Shaped Phosphane in the Rhodium-Catalyzed Hydrosilylation of Ketones, Angew. Chem., Int. Ed, 2003, 42, 1287-1289 2003, 115, 1325-1327, 2003.01.
128.	Wakatsuki, Y.; Hou, Z.; Tokunaga, M., New Reactions of 1-Alkynes Catalyzed by Transition Metal Complexes, The Chemical Record, 2003, 3, 144-157, 2003.01.
129.	Obora, Y.; Moriya, H.; Tokunaga, M.; Tsuji, Y, Cross-coupling Reaction of Thermally Stable Titanium(II)-alkyne Complexes with Aryl Halides Catalysed by a Nickel Complex, ChemComm., 2003.01.
130.	Iwasawa, T.; Tokunaga, M.; Obora, Y.; Tsuji, Y, Homogeneous Palladium Catalyst Suppressing Pd Black Formation in Air Oxidation of Alcohols, J. Am. Chem. Soc, 2004, 126, 6554-6555, 2004.01.
131.	Aoyama, H.; Tokunaga, M.; Hiraiwa S.; Shirogane, Y.; Obora, Y.; Tsuji, Y, Hydrolysis of Alkenyl Esters and Ethers Catalyzed by Metal Complexes, Org. Lett, 2004, 6, 509-512, 2004.01.
132.	Obora, Y.; Kimura, M.; Tokunaga, M.; Tsuji, Y, Low-valent Nb(III)-mediated synthesis of 1,1,2-trisubstituted-1H-indenes from aliphatic ketones and aryl-substituted alkynes, ChemComm, 2005, 901 - 902, 2005.01.
133.	Obora, Y.; Liu, Y.- K.; Jiang, L.-H.; Takenaka, K.; Tokunaga, M.; Tsuji, Y, Iridium(I) and Rhodium(I) Cationic Complexes with Triphosphinocalix[6]arene Ligands: Dynamic Motion with Size-Selective Molecular Encapsulation, Organometallics, 2005, 24, 4-6, 2005.01.
134.	Komano, T.; Iwasawa, T.; Tokunaga, M.; Obora, Y.; Tsuji, Y, MALDI TOF Mass Study on Oligomerization of Pd(OAc)2(L)2 (L=Pyridine Derivatives):Relevance to Pd Black Formation in Pd-catalyzed Air Oxidation of Alcohols, Org. Lett, 2005, 7, 4677-4679, 2005.01.
135.	徳永　信, 水やアミンを反応剤に用いる位置および立体選択的反応, 有機合成化学協会誌, 2005, 63, 20-27, 2005.01.
136.	Fujihara, T.; Obora, Y.; Tokunaga, M.; Sato, H.; Tsuji, Y, Dendrimer N-Heterocyclic Carbene Complexes with Rhodium(I) at the Core, ChemComm., 2005, 4526 - 4528, 2005.01.
137.	Aoyama, H.; Tokunaga, M.; Kiyosu, J.; Iwasawa, T.; Obora, Y.; Tsuji, Y, Kinetic Resolution of Axially Chiral 2,2’-Dihydroxy-1,1’-biaryls by Palladium Catalyzed Alcoholysis, J. Am. Chem. Soc, 2005, 127, 10474-10475, 2005.01.
138.	Niyomura, O.; Iwasawa, T.; Sawada, N.; Tokunaga, M.; Obora, Y.; Tsuji, Y, A Bowl-Shaped Phosphine as a Ligand in the Rhodium-Catalyzed Hydrosilylation — Rate Enhancement by a Mono-phosphine Rhodium Species, Organometallics, 2005, 24, 3468-3475, 2005.01.
139.	Tokunaga, M.; Shirogane, Y.; Aoyama, H.; Obora, Y.; Tsuji, Y, Copper-catalyzed oxidative cleavage of carbon-carbon double bond of enol ethers with molecular oxygen, J. Organomet. Chem, 2005, 690, 5378-5382. (special issue, Organometallic Chemistry - The Next Generation), 2005.01.
140.	Obora, Y.; Tokunaga, M.; Tsuji, Y, Transition–metal Complexes with Nano–sized Phosphine and Pyridine Ligands–Catalysis, Fluxional Behavior and Molecular Recognition, Catalysis Survey from Asia, 2005, 9, 259-268, 2005.01.
141.	Obora, Y.; Kimura, M.; Ohtake, T.; Tokunaga, M.; Tsuji, Y, Nickel–Catalyzed Cross–Coupling Reaction of Niobium(III)–Alkyne Complexes with Aryl Iodides, Organometallics, 2006, 25, 2097-2100, 2006.03.
142.	Tokunaga, M.; Kiyosu, J.; Obora, Y.; Tsuji, Y, Kinetic Resolution Displaying Zeroth Order Dependence on Substrate Consumption: Copper-catalyzed Asymmetric Alcoholysis of Azlactones, J. Am. Chem. Soc, 2006, 128, 4481-4486, 2006.04.
143.	Obora, Y.; Liu, Y.- K.; Kubouchi, S.; Tokunaga, M.; Tsuji, Y, Monophosphinocalix[6]arene Ligands—Synthesis, Characterization, Complexation, and Their Use in Catalysis, Eur. J. Inorg. Chem, 2006, 222-230, 2006.04.
144.	Iwasawa, T.; Komano, T.; Tajima, A.; Tokunaga, M.; Obora, Y.; Fujihara, T.; Tsuji Y., Phosphines having a 2,3,4,5-tetraphenylphenyl moiety: effective ligands in palladium-catalyzed transformations of aryl chlorides, Organometallic, 2006.06.
145.	Tokunaga, M.; Aoyama, H.; Shirogane, Y.; Obora, Y.; Tsuji, Y., Oxidative cleavage of C–C bond of 2-phenylpropionaldehyde using molecular oxygen., Catalysis Today, 2006, 117, 138-140, 2006.07.
146.	Murai, T.; Inaji, S.; Morishita, K.; Shibahara, F.; Tokunaga, M.; Obora,Y.; Tsuji Y., Synthesis of 1,1'-Binaphthyl-2,2'-diyl Phosphoroselenoic Amides and Their Conversion to Optically Pure Phosphoramidites, Chem. Lett.,, 35, 1424-1425., 2006.12.
147.	Ohta, H.; Tokunaga, M.; Obora, Y.; Iwai, T.; Iwasawa, T.; Fujihara,, A Bowl-Shaped Phosphine as a Ligand in Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Chlorides: Effect of a Depth of the Bowl, Org. Lett.,2007, 9, 89-92, 2007.04.
148.	Sato, H.; Fujihara, T.; Obora, Y.; Tokunaga, M.; Kiyosu, J.; Tsuji Y., Rhodium(I) complexes with N-heterocyclic carbenes bearing a 2,3,4,5-tetraphenyl-phenyl and its higher dendritic frameworks, ChemComm.,, ChemComm.,, 2007.04.
149.	Tokunaga, M.; Aoyama, H.; Kiyosu, J; Shirogane, Y.; Iwasawa, T.; Obora,, Metal complexes-catalyzed hydrolysis and alcoholysis of organic substrates and their application to kinetic resolution, J. Organomet. Chem., 692, 472-480., 2007.01.

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