Researchers Database

KATAOKA Yasutaka

FacultyFaculty Division of Natural Sciences Research Group of Chemistry
PositionProfessor
Last Updated :2024/02/22

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Profile and Settings

  • Name (Japanese)

    Kataoka
  • Name (Kana)

    Yasutaka

Research Areas

  • Nanotechnology/Materials, Synthetic organic chemistry

Research Experience

  • Mar. 2005, 奈良女子大学理学部教授
  • Feb. 2002, 大阪大学大学院基礎工学研究科助教授
  • Jul. 2000, 大阪大学大学院基礎工学研究科講師
  • Apr. 1997, Sep. 1998, 日本学術振興会海外特別研究員(米国マサチューセッツ工科大学化学科、Buchwald 教授)
  • Sep. 1998, 大阪大学大学院基礎工学研究科助手
  • Apr. 1992, 大阪大学基礎工学部助手
  • Apr. 1990, Mar. 1992, 日本学術振興会特別研究員

Education

  • 1992, Kyoto University, Graduate School, Division of Engineering, 工業化学専攻
  • 1987, Kyoto University, Faculty of Engineering, 工業化学科

Association Memberships

  • 日本化学会
  • 錯体化学会
  • 近畿化学協会
  • 米国化学会

Ⅱ.研究活動実績

Published Papers

  • Refereed, 41, 2810, 2821
  • Refereed, 20, 570, 574
  • Refereed, 10, 3285, 3289
  • 10 2020, 56, 12977, 12980, OI: 10.1039/D0CC05572G
  • Refereed, Organometallics, American Chemical Society (ACS), Synthesis of Pd-NNP Phosphoryl Mononuclear and Phosphinous Acid-Phosphoryl-Bridged Dinuclear Complexes and Ambient Light-Promoted Oxygenation of Benzyl Ligands, Yuma Shigehiro; Karen Miya; Risa Shibai; Yasutaka Kataoka; Yasuyuki Ura, 26 Sep. 2022, 41, 19, 2810, 2821, Scientific journal, 10.1021/acs.organomet.2c00399
  • Refereed, Organic & Biomolecular Chemistry, Royal Society of Chemistry (RSC), Synthesis of 2-hydroxytetrahydrofurans by Wacker-type oxidation of 1,1-disubstituted alkenes, Rina Tanaka; Saki Komori; Yuhei Shimizu; Yasutaka Kataoka; Yasuyuki Ura, 2-Hydroxytetrahydrofurans were synthesized by Wacker-type oxidation of 3-methyl-3-buten-1-ols with high stereoselectivity, using a PdCl2(MeCN)2/NO/BQ catalyst system under O2., 22 Dec. 2021, 20, 3, 570, 574, Scientific journal, 10.1039/d1ob02277f
  • Refereed, Asian Journal of Organic Chemistry, Wiley, Palladium‐Catalyzed Aerobic α,β‐Dehydrogenation of Carboxylic Acids, Ayaka Shibatani; Yasutaka Kataoka; Yasuyuki Ura, 13 Oct. 2021, 10, 12, 3285, 3289, Scientific journal, 10.1002/ajoc.202100637
  • Refereed, ChemCatChem, Palladium/Copper-catalyzed Oxidation of Aliphatic Terminal Alkenes to Aldehydes Assisted by p-Benzoquinone, Saki Komori; Yoshiko Yamaguchi; Yuka Murakami; Yasutaka Kataoka; Yasuyuki Ura, © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The development of an anti-Markovnikov Wacker-type oxidation for simple aliphatic alkenes is a significant challenge. Herein, a variety of aldehydes can be selectively obtained from various unbiased aliphatic terminal alkenes using PdCl2(MeCN)2/CuCl in the presence of p-benzoquinone (BQ) under mild reaction conditions. Isomerization of the terminal alkene to the internal alkene was suppressed via slow addition of the starting material to the reaction mixture. In addition to the Pd catalyst, CuCl and BQ were essential in order to obtain the anti-Markovnikov product with high selectivity. Terminal alkenes bearing a halogen substituent afforded their corresponding aldehydes with high anti-Markovnikov selectivity. The halogen acts as a directing group in the reaction. DFT calculations indicate that a μ-chloro Pd(II)−Cu(I) bimetallic species with BQ coordinated to Cu is the catalytically active species in the case of a terminal alkene without a directing group., 06 Aug. 2020, 12, 15, 3946, 3955, Scientific journal, 10.1002/cctc.202000472
  • Refereed, Chem. Commun., Secondary Phosphine Oxide-triggered Selective Oxygenation of a Benzyl Ligand on Palladium, Oka, Sayaka; Shigehiro, Yuma; Kataoka, Yasutaka; Ura, Yasuyuki, 2020, 56, 12977, 12980
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, Preferential geometry and reactivity of neutral iridium(III) and rhodium(III) complexes bearing a flexible heterochelate PN ligand (PN = o-Ph2PC6H4CH2OCH2C5H4N-2), Takeshi Hara; Tsuneaki Yamagata; Kazushi Mashima; Yasutaka Kataoka, Reactions of [IrCl(coe)(2)](2) (coe = cyclooctene) with 1 equiv of the PN ligand (PN = o-Ph2PC6H4CH2OCH2C5H4N-2) in the presence of several phosphines or pyridine (1 equiv) at room temperature afforded a neutral iridium(III) hydride complex, (PCN-kappa P-3,C,N)Ir(H)(Cl)(L) (PCN = Ph2PC6H4CHOCH2C5H4N) [L = PPh3 (1a), PCy3 (1b), PBu3 (1c), PMePh2 (1d), Py (1e)] in good isolated yield. The PCN ligand is coordinated in a meridional manner, which was confirmed by spectral analyses and X-ray analysis of 1a. The related rhodium(III) hydride complex (PCN-kappa P-3,C,N)Rh(H)(Cl)(L) (PCN = Ph2PC6H4CHOCH2C5H4N) [L = PPh3 (4a), PCy3 (4b)] was also prepared from the reactions of [RhCl(coe)(2)](2) with 1 equiv of the PN ligand in the presence of 1 equiv of PPh3 or PCy3. The structure of 4a and 4b was determined by spectral analyses and X-ray analysis of 4a. In contrast to the iridium complexes, the PCN ligand in the rhodium(III) complexes coordinated to the metal center in a facial manner. A ligand exchange reaction of the PPh3 iridium(III) complex 1a with PCy3 did not proceed well (20% conversion), while a similar reaction of the PPh3 rhodium(III) complex 4a with PCy3 afforded the PCy3 complex 4b quantitatively. We examined the ligand exchange reactions of the iridium(III) and rhodium(III) complexes with various phosphines to explain the different reactivities. Using Tolman's parameter, we demonstrated that the ligand exchange reaction in the iridium(III) complexes bearing the meridional-coordinated PCN ligand is controlled by the steric factor of the phosphines and the ligand exchange reaction in the rhodium(III) complexes bearing the facial-coordinated PCN ligand is controlled by their electronic factors. The meridional coordination of the PCN ligand makes the environment around the iridium center sensitive to the steric nature due to the steric repulsion between the diphenyl group in the PCN ligand and the phosphines. The facial coordination of the PCN ligand decreases their repulsion, and reactivity of the metal center depends on the basicity of the phosphines., Jan. 2007, 26, 1, 110, 118, Scientific journal, 10.1021/om060405d

MISC

  • Not Refereed, Organometallics, Oxidative Addition of RCO2H and HX to Chiral Diphosphine Complexes of iridiumu(I): Convenient Syntheses of Mononuclear Halo-Carboxylate Iridium(III) Complexes and Cationic Dinuclear Triply Halogen-Bridged iridium(III) Complexes and their Catalytic Per・・・, 片岡 靖隆; T. Yamagata; H. Tadaoka; M. Nagata; T. Hirao; Y. Kataoka; V. Ratovelomanana-Vidal; J. P. Genet; K. Mashima, Oxidative Addition of RCO2H and HX to Chiral Diphosphine Complexes of iridiumu(I): Convenient Syntheses of Mononuclear Halo-Carboxylate Iridium(III) Complexes and Cationic Dinuclear Triply Halogen-Bridged iridium(III) Complexes and their Catalytic Performance in Asymmetric Hydrogenation of Cyalic Imines and 2-Phenylquinoline, 2006, 25, 10, 2505, 10.1021/om051065j
  • Not Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, Oxidative addition of RCO2H and HX to chiral diphosphine complexes of iridium(I): Convenient synthesis of mononuclear halo-carboxylate iridium(III) complexes and cationic dinuclear triply halogen-bridged iridium(III) complexes and their catalytic performance in asymmetric hydrogenation of cyclic imines and 2-phenylquinoline, Tsuneaki Yamagata; Hiroshi Tadaoka; Mitsuhiro Nagata; Tsukasa Hirao; Yasutaka Kataoka; Virginie Ratovelomanana-Vidal; Jean Pierre Genet; Kazushi Mashima, Mononuclear iridium(III) complexes of general formula IrX(H)(O2CR)[(S)-binap] (2, R = CH3; 3, R = Ph; 4, R = C6H4CH3-p; a, X = Cl; b, X = Br; c, X = 1) were prepared by one-pot reaction of [Ir(mu-X)(cod)12 with 2 equiv of (S)-BINAP [=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] and an excess of the corresponding carboxylic acid in toluene. The structure of (S)-2-4 bearing an (S)-BINAP was confirmed to be OC-6-23-A (Lambda-conformation) by X-ray analysis of (S)4a-c. In this reaction, the iridium(1) complex (I) {Ir(mu-Cl)[(S)-binap]}(2) [(S)-5a] and pentacoordinated iridium(l) complexes IrX(cod)[(S)-binap] [(S)-7b, X = Br; (S)-7c, X = I] were generated prior to the oxidative addition of carboxylic acid. Cationic inuclear iridium(III) complexes of general formula [{Ir(H)[(S)-binap]}(2) (mu-X)(3)]X [(S)-8: a, X = Cl; b, X = Br; c, X = 1] were prepared, and their cationic bifacial octahedral dinuclear structure was characterized by spectral data and combustion analysis. The anionic portion of these complexes could be replaced by NaPF6, leading to the corresponding PF6 salts [{Ir(H)[(S)-binap]}(2)(mu-X)(3)]PF6 [(S)-8: d, X = Cl; e, X = Br; f, X = I]. Iodo-acetate complexes of p-TolBINAP (=2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl) [(S)-9c] and SYNPHOS [=2,2',3,3'-tetrahydro(5,5'-bi-1,4-benzodioxin)-6,6'-diyl]bis(diphenylphosphine)] [(S)40c] were also prepared according to the method used for the BINAP complex (S)-2c and were characterized spectroscopically. Cationic dinuclear complexes of p-TolBINAP [(S)-11c] and SYNPHOS [(S)-12c] were also generated. Using these complexes, the effect of halide variation was studied by asymmetric hydrogenation of 2-phenylpyrrolidine (13) and 2-phenyl-4,5,6,7-tetrahydro-3H-azepine (15) along with 2-phenylquinoline (16), and the results indicated that iodide complexes were better catalyst precursors for catalytic activity than the corresponding chloride and bromide complexes, but were not superior in enantioselectivity., May 2006, 25, 10, 2505, 2513, 10.1021/om051065j
  • Not Refereed, ORGANIC LETTERS, AMER CHEMICAL SOC, Asymmetric transfer hydrogenation of aryl ketones catalyzed by salt-free two samarium centers supported by a chiral multidentate alkoxy ligand, K Ohno; Y Kataoka; K Mashima, We synthesized a chiral multidentate ligand, (R,R,R,R)-N,N,N',N'-tetra(2-hydroxy-2-phenylethyl)-1,3-xylylene diamine [(R)-2], which can support two metals at adjacent positions. Asymmetric transfer hydrogenation of acetophenone and its derivatives was conducted by using salt-free bimetallic lanthanoid complexes of (R)-2, and the combination of two samarium atoms and (R)-2 was found to be the best catalyst system for asymmetric transfer hydrogenation of aryl ketones in high enantioselectivity (up to >99% ee)., Dec. 2004, 6, 25, 4695, 4697, 10.1021/ol048101f
  • Not Refereed, ORGANIC LETTERS, AMER CHEMICAL SOC, Asymmetric transfer hydrogenation of aryl ketones catalyzed by salt-free two samarium centers supported by a chiral multidentate alkoxy ligand, K Ohno; Y Kataoka; K Mashima, We synthesized a chiral multidentate ligand, (R,R,R,R)-N,N,N',N'-tetra(2-hydroxy-2-phenylethyl)-1,3-xylylene diamine [(R)-2], which can support two metals at adjacent positions. Asymmetric transfer hydrogenation of acetophenone and its derivatives was conducted by using salt-free bimetallic lanthanoid complexes of (R)-2, and the combination of two samarium atoms and (R)-2 was found to be the best catalyst system for asymmetric transfer hydrogenation of aryl ketones in high enantioselectivity (up to >99% ee)., Dec. 2004, 6, 25, 4695, 4697, 10.1021/ol048101f

Books etc

  • O-H Bond Activation and Addition to Unsaturated Sysems, Wiley-VCH, KATAOKA Yasutaka; Y. kataoka; K. Tani, 分担, 2001, 171-213, Not Refereed

Research Projects

  • 遷移金属錯体を利用した有機合成反応の開発, 0, 0, 0, Competitive research funding
  • 有機金属錯体の合成, 0, 0, 0, Competitive research funding
  • Grant-in-Aid for Scientific Research (C), 2003, 2005, 15550091, Development of asymmetric C-H bond activation mediated by new transition metal complexes having a metal centered chirality, KATAOKA Yasutaka, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, 3700000, 3700000, 1.We have developed a new method for the construction of a stereogenic center on the metal by the diastereoselective addition of the Meerwein reagent (Me_3OBF_4) to rhodium carbonyl complexes having the Cp'-P ligand, [{3-(R)Ind-P}_]H [R = H(a), Et(b), Cy(c), 1'S,2'S,5'R-neomenthyl (NM) (d), 1'R,2'R,5'R-neoisomenthyl (NIM) (e)], in which an indenyl group having a substituent (R) at the 3-position and a diphenylphosphino group are connected by an ethylene group. 2.The Index ligands, in which an indenyl group and an oxazoline ring are connected by an ethylene or propylene spacer, have been designed and their iridium(III) and rhodium(III) cationic complexes having a stereogenic center at the metal have been prepared stereoselectively by the ligand exchange reaction of their neutral complexes bearing two prochiral iodido ligands with AgOTf. 3.We would like to show the preparation of π-allyl iridium(III) and rhodium(III) complexes having the Cp'-P ligand by using the oxidative addition method. In this case, if a substituent is attached to one of the terminal carbons of the π-allyl ligand, the π-allyl complexes bearing the Cp'-P ligand have a chirality on the metal center. In other words, control of the coordination mode of the p-allyl ligand in the complexes bearing the Cp'-P ligand is the same meaning as control of the stereochemistry around a stereogenic center arising at the metal. Since several substituents are easily introduced at the 3-position of the indenyl group of the Cp'-P ligand, we examined the effect of the substituent to the selectivity of π-allyl complexes. Higher selectivity of the major isomer was obtained when bulkier substituents were introduced at the indenyl group in the Cp'-P ligand., kaken
  • Grant-in-Aid for Scientific Research (A), 2000, 2001, 12355032, Development of Practical Catalytic Asymmetric Hydrogenatioh Using Methanol as a Hydrogen Source, TANI Kazuhide; YAMAGATA Tsuneaki; KATAOKA Yasutaka; MASHIMA Kazushi; SAYO Noboru; KUMOBAYASHI Hidenori, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Osaka University, 35320000, 32800000, 2520000, In this project, we studied O-H activation with late-transition metal complexes. We have found that [Ir(μn-Cl)(binap)]_2 (1) can easily activate methanol and the complex 1 and its oxidative addition complex of methanol act as efficient hydrogenation catalyst precursors of alkyne using methanol as a hydrogen source. Although these Complexes act as catalyst precursors for asymmetric hydrogenation of prochiral olefins also, their catalytic activity was not high enough and the enantio-selectivity for hydrogenation of dehydroamino acids remained as high as 50 %ee. Complex 1 can also activate various kinds of carboxylic acids very easily and (S)-1 gave quantitatively and stereoselectively, mononuclear hydrido(carboxylato) complexes (S)-OC-6-23-A-[Ir(Cl)(H)(h^2-0_2CR){(S)-binap}] (R=Me, Ar) (2), among five possible stereoisomers. Complexes 2 were found very efficient catalyst precursors for asymmetric hydrogenation of imine. Especially, for hydrogenation of cyclic imines, very high optical induction over 99 %ee was realized. So-called a neutral rhodium-diphosphine catalyst, "RhCl(diphosphine)", has been prepared in situ and used in many kinds of catalysis, but its isolation is rare and the complex has not been well characterized. We have succeeded in isolation and full characterization including X-ray analysis of the rhodium analogue of complex 1, [Rh(μ-Cl){(S)-binap}]_2 (3). Complex 3 has a very similar structure to that of 1 but the properties of 3 were very much different from those of complex 1 ; Complex 1 is very sensitive against air as well as protic molecules but complex 3 was inert against these substances even at heating conditions. As complex 3 is considered to be effective for activation of dihydrogen, more detailed studies on Complex 3 will be needed. A comparative studies between complexes 1 and 3 would provide useful information about their applications. In addition, we contributed a review article about O-H activation to a book, "Catalytic Heterofunctionalization" edited by A. Togni and H. Grutzmacher and published by Wiley-VCH., kaken
  • Grant-in-Aid for Scientific Research (C), 1999, 2001, 11650894, Development of Novel Catalytic systems Using by the Cp'-P Ligand Having a Planar Chirality, KATAOKA Yasutaka, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Osaka University, 3400000, 3400000, I have been working on chemistry of transition metal complexes having the Cp'-P ligand. The Cp'-P ligand has both a cyclopentadienyl derivatives and a tertiary phosphine group connected by an appropriate spacer. The complexes having Cp'-P ligand are expected to show the combination character of cyclopentadienyl complexes and phosphino complexes. Addition of them, we can disclose an interesting behavior of the Cp'-P ligand through our research. In this project, I can find some interesting results obtained by using the Cp'-P ligand. Main points are shown the followings. First, I have prepared the several kinds of Cp'-P ligand and examined their characters. We can find out that the combination of planar chirality and stereogenic center on the substituent was very effective for controlling the chirality on Rh center. Second, we have obtain experimental evidence for migration of an alkyl group in migratory insertion and retro-Migratory Insertion by using the three-legged piano-stool rhodium Complex having Cp'-P Ligand. Third, as an application to organic synthesis, I have developed stereo- and regio selective acylmethylation of alkynes mediated by the Cp'-P Rh complexes., kaken
  • Grant-in-Aid for Scientific Research (B)., 1998, 2000, 10440207, Generation of Organometallic Conjugated Compounds Applicable for Non-linear Optics, MASHIMA Kazushi; KATAOKA Yasutaka; YAMAGATA Tsuneaki, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Osaka University, 12700000, 12700000, The construction of linear covalently-linked metal clusters has attracted much interest in view of fundamental bonding as well as promising applications as extensive electronic communications and optoelectronic materials. We have already reported synthesis and reaction of a linearly aligned tetranuclear complex, Mo_2Pd_2(pyphos)_4 (1)(pyphos=6-diphenylphosphino-2-prydonate), which was prepared by treating a quadruply bonded dinuclear dimolybdenum (II) complex, Mo_2(pyphos)_4 (2), with Pd_2(dba)_3(C_6H_6) in THF.The most interesting feature is that both Pd(O) atoms of 1 datively interacted with the Mo_2 core and hence the Pd(O) centers, unlike normal monoculear Pd(O) complexes, reacted oxidatively with dichloromethane at room temperature to give a Pd(II) complex, Mo_2PdCl_2(CH_2Cl)_2(pyphos)_4 (3). On monitoring the reaction of equation 1 by UV spectroscopy, the deep orange color (λ_=476 nm) of 1 in dichloromethane turned immediately to greenish brown [the Pd(I) complex, Mo_2Pd_2Cl_2(pyphos)_4 (4) was deep green (λ_=642 nm)], and then gradually resulted in the formation of the Pd(II) complex 3. We found that disulfides oxidatively added to both Pd(O) metals of 1 in a 1,4-addition reaction ; 1 reacted with one equivalent of diaryldisulfides in THF at room temperature to give the corresponding Pd(I)-thiolate complexes, Mo_2Pd_2(pyphos)_4(SAr)_2 (5a-f) in modest yields. Multiply-bonded tetranuclear complexes M_2Pd_2Cl_2(pyphos)_4 (6) and dinuclear complexes M_2(pyphos)_4 (7) (a, M=Mo ; b, M=Cr ; pyphos=6-diphenylphosphino-2-pyridonate) are found to exhibit large hyperpolarizability γ of nonlinear optical property by using the picosecond degenerate four-wave mixingg (DFWM) method ; the γ values of 6a (1.5×10^<-30> esu), 6b (5.2×10^<-31> esu), and 7a (6.9×10^<-31> esu) are greater than those (ca.10^<-35>-10^<-33> esu) of transition metal poly(yne) polymers. Recent development of the polymerization chemistry based on well-defined organometallic complexes is remarkable. Coordination polymerization of polar olefinic monomers such as methyl acrylate (MA) and methyl methacrylate (MMA) has been accomplished by using various enolate complexes. In this contribution, we would like to report the first Group 5 metal complex active for MMA polymerization. Moreover, we present our new idea to generate a catalytically active enolate complex from an organometallic complex bearing a polar monomer as a ligand. The coordinated MMA ligands of newly prepared tantalum complexes TaCp^*(η^2-p-MeOC_6H_4-DAD)(η^4supine-MMA)(8) (p-MeOC_6H_4-DAD=1,4-bis(p-methoxyphenyl)-1,4diaza-1,3-butadiene) and TaCp^*(η^2-Cy-DAD)(η^4-supine-MMA)(9) (Cy-DAD=1,4-dicyclohexyl-1,4-diaza-1,3-butadiene) were activated by addition of one equivalent of AlMe_3 to generate active catalysts for polymerization of MMA.The catalyst system of the highest activity was the combination of 9 and one equiv of AlMe_3 at -20℃ ; the polymerization completed within 10 min to give a PMMA with very narrow polydispersity (M_w/M_n=1.10)., kaken
  • Grant-in-Aid for Scientific Research (A)., 1997, 2000, 09309006, Development of Selective Organic Synthesis and Catalysis Based on Characteristics of Organotransition Compounds, TANI Kazuhide; YAMAGATA Tsuneaki; KATAOKA Yasutaka; MASHIMA Kazushi, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Osaka University, 31000000, 31000000, With the aim of discovering new organic synthesis and catalysis based on characteristics of organotransition metal compounds we performed the research project. The following new results were obtained. 1) Neutral iridium diphosphine complexes carrying peraryldiphosphines, [IrCl (diphosphine)]_2, can activate easily O-H bonds of alcohol, water, etc to produce their oxidative addition products. The complex is an efficient catalyst for transfer hydrogenation of unsaturated compounds using methanol as a hydrogen donor. 2) Low valent vanadium(II) compounds are useful reagents for selective alkylation, allylation, C-C bond formation accompanying C-O bond cleavage of carbonyl compounds. 3) General method of preparation of complexes Tp^*MCl_nL_O {Tp^*=hydrotris (pyrazolyl) borates, M=group 4-6 transition metal} using Tp^*SnR_nCl_<3-n> (R=alkyl) as a Tp^* transfer reagent was provided 4) New optically active Cp'-P ligands, containing both an indenyl group carrying an optically active substituent and a diphenylphosphino group connected by an alkylene spacer, were synthesized and their stereoselective rhodium complexes regulating the panar as well as the central chirality were prepared. A theoretical catalytic cycle for selective formation of α, β-unsaturated ketones from acetylene, CO, methyl iodide and trimethyl aluminum with (Cp'-P)Rh(CO) as a catalyst was established. 5) A coordinatively flexible P-N ligand which has a diphenylphosphino group and a 2-pyridyl group connected by an oxaalkylene chain was synthesized. Direct observation of reversible oxidative addition and reductive elimination of C(sp^3)-H bonds was accomplised by using the iridium complexes of the P-N ligand. 6) A series of 1,4-diazadiene complexes of niobium and tantalum have been prepared. These complexes becom active catalysts for polymerization of MMA.By choosing ancillary ligands, 1,4-diazadiene can coordinate to a metal in several different coordination geometry, planar σ^2-, prone and supine nonplanar σ^2, π-enediamide. Tacticity and polydispersity of PMMA could be regulated., kaken
  • 特定領域研究(A), 1998, 1998, 10125222, 炭素-ヘテロ原子二重結合の錯体触媒を用いた不斉水素化, 谷 一英; 山縣 恒明; 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 2100000, 2100000, 1. 我々は、イリジウム(I)-BINAP(2,2'-ビス(ジフェニルホスフィノ)-1.1'-ピナフチル)-1級または2級アミンからなる触媒系がメタノール中イミンの不斉水素化に効果的であることを見いだしている。この触媒反応の反応機構解明のため、触媒系の前駆体である、[IrCl(binap)]_2と種々のプロトン性化合物との反応を検討した。その結果、メタノール、水、カルボン酸、チオールのO-H結合あるいはS-H結合が活性化され、イリジウムに酸化敵付加したカチオン性のヒドリド(メトキソ)、ヒドリド(ヒドロキソ)、ヒドリド(カルボキシラート)、およびヒドリド(チオラート)二核イリジウム(I)錯体が高取率で得られた。 2. [IrCl(binap)]_2と触媒系の添加剤である1級ベンジルアミンおよび、その誘導体との反応を検討した。[IrCl(binap)]_2とベンジルアミン誘導体を、トルエン溶媒中70℃で3時間反応させると、オルトメタル化したヒドリドアリール錯体のジアステレオマー混合物が、白色粉末として定量的に得られた。その構造を^1Hおよび^<31>P{^1H}NMRスペクトル、2次元COSYおよびNOESYを用いて明らかにした。 3. ヒドリド(カルボキシラート)イリジウム(I)錯体を用いると、6員環環状イミンの不斉水素化において最高93%代の高い光学収率で対応するアミンが得られた.この錯体を用いると従来必要であった活性な触媒系創出のための前処理が必要でなくなる。また、アミンを添加しなくても高収率、高選択的に水素化反応が進行するので、生成物であるアミンを簡便に単離することができた。また、この触媒系は基質に対する特異性が高く、目的の炭素ー窒素二重結合のみを選択的に還元することができる., kaken
  • 重点領域研究, 1997, 1997, 09231232, 炭素-ヘテロ原子二重結合の錯体触媒を用いる不斉水素化, 谷 一英; 山縣 恒明; 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 2000000, 2000000, Ir(I)/BINAP or tol-BINAP/RNH_2 or RR'NHからなる触媒系がメタノール溶媒中イミンの良好な不斉水素化触媒となることを明らかにした。高い不斉収率の達成には一級あるいは二級アミンの添加が必須であるが、添加アミンのキラリティーは不斉収率には全く影響を与えなかった。また、反応を再現性よく進行させるためには触媒を調整した後室温、アルゴン下で1時間程度のインキュベーションが必要である。鎖状イミンの還元では最高77%eeの不斉選択性が達成出来たが、幾何異性体の存在しない環状六員環イミン2-pheny1-3,4,5,6-tetrahydropyridineでは90%eeと非常に高い不斉収率が達成された。窒素原子上に光学活性α-phenethy1基を有するキラルイミンを基質に用いると、鎖状イミンでも最高99%deの非常に高いジアステレオ選択性で光学活性アミンが得られた。α-phenethy1基は加水素化分解で容易に除去出来るのでプロキラルなケトンと入手容易な光学活性α-phenethylamineから高い光学純度の種々の光学活性アミンが得られることになる。本触媒系の活性種の情報を得るため[IrCl(cod)]_2とBINAPとの反応で空気に非常に不安定で反応活性な塩素架橋2核錯体[IrCl(binap)]_2の単離に成功し、そのX-線構造解析を行った。また本錯体は種々のプロトン性分子を容易に活性化し、例えば室温でメタノールを酸化的付加し、ヒドリド(メトキソ)錯体[{Ir(H)(binap)}_2(μ-OMe)_2(μ-Cl)]Clを高収率で与えることを見出し、そのX-線解析で構造を明らかにした。これらの錯体はいずれも本触媒反応の活性種と深くかかわった錯体と考えられる。, kaken
  • 奨励研究(A), 1996, 1996, 08751006, 低原子価バナジウムを用いた脱酸素・脱硫黄を伴う炭素骨格構築反応, 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 1000000, 1000000, 低原子価バナジウムを用いた、カルボニル化合物からの脱酸素を伴う炭素-炭素単結合が生成するカップリング反応の開発に成功した。カルボニル化合物にグリニヤール反応剤やアルキルリチウムを反応させ調製したアルコキシマグネシウム、あるいはリチウム錯体に2価のバナジウムを作用させアルコキシバナジウムを系中に発生させる。そこに、触媒量の分子酸素存在下加熱環流すると、脱酸素を伴ったカップリング反応が進行する。本反応の特徴は次の2点である。まず1点目は、いわゆる前周期遷移金属を用いたカルボニル化合物のカップリング反応は、炭素-炭素2重結合ができるのに対し、本反応では、炭素-炭素単結合が生成するところである。2点目は、触媒量の分子酸素を必要としていることである。酸素が存在しないとこのカップリング反応は進行しない。また、酸素の量が多すぎても進行しない。様々なバナジウム錯体を検討した結果、脱酸素には低原子価のバナジウムと触媒量の高原子価のバナジウムの両方が必要であることがわかった。 この反応を脱硫黄を伴うカップリング反応に応用した。ベンジルチオールのリチウム塩に2価のバナジウムを作用させ加熱環流すると脱硫黄を伴ったカップリング反応が進行する。また、反応系中にα,β-不飽和ケトンを共存させると、脱硫黄を伴ったマイケル付加反応が進行した。現在のところ、反応が進行するチオールはα-置換ベンジルチオールに限られている。今後、窒素系の不斉配位子をバナジウムに導入し、不斉反応へ応用する予定である。, kaken
  • 奨励研究(A), 1995, 1995, 07750954, 低原子価バナジウムを用いる四級炭素形成反応の開拓., 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 900000, 900000, 低原子価の金属を用いたカルボニル化合物のモノアリル化反応は、莫大な研究例があり、その成果は、ほぼ完成の域に達しているといっても過言ではない。しかし、低原子価のバナジウムを用いたアリル化反応の例はない。その理由として、II価のバナジウムは、臭化アリルを容易に還元する能力を有しているが、それにより生成するアリルバナジウム化合物は非常に不安定で、すぐ臭化アリルの二量化反応が進行する、と言うことがあげられる。低原子価バナジウムと臭化アリルの組み合わせによる反応を設計するとき、いかにアリルバナジウムを安定に系中に発生させるか、また、いかに二量化する前に反応を起こさせるか、と言う問題点を解決しなくてはならない。これらのことを踏まえ、臭化アリルとII価のバナジウムとの組み合わせについて検討した結果、カルボニル化合物から酸素の脱離を伴い一段階でカルボニル炭素を四級炭素に変換する方法を見いだした。 プロピオフェノンにMeMgBrを作用させた後、単離可能な単核のII価のバナジウム錯体VCl_2(tmeda)_2と臭化アリルを加え加熱還流すると、プロピオフェノンのカルボニル基の酸素が脱離し、メチル基とアリル基が導入された四級炭素生成物が得られた。反応機構は次のように考えられる。まず、プロピオフェノンとMeMgBrから生成するアルコキシマグネシウムと二価のバナジウムが金属変換しアルコキシバナジウムができる。それが臭化アリルを還元しアリルアルコキシバナジウムが生成する。その後、バナジウムが酸素を伴って脱離し分子内でカップリング反応が生じ、四級炭素化合物ができる。本反応は、他の価数(三価、四価)のバナジウム錯体やクロム、チタンなどの他の低原子価金属を用いても全く進行せず、バナジウム二価特有の反応であることが分かった。今後、不斉配位子を有するバナジウム錯体を合成し、不斉反応に応用する予定である。, kaken
  • 重点領域研究, 1995, 1995, 07214220, 新規光学活性シクロペンタジエニル錯体の合成と不斉触媒への応用, 谷 一英; 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 1900000, 1900000, 我々はシクロペンタジエニル基とホスフィノ基がL-threitol誘導体の骨格でキレートされた新規光学活性二座配位子を開発し、そのルテニウム錯体がアセチレン化合物とアリルアルコールの不斉カップリング反応に応用できることを明らかにしてきた。今回はまず、光学活性Cp-p配位子を有する(Cp-P)RuCl(PPh^3)とNaOMeから調製したCp-Pルテニウムヒドリド錯体(Cp-P)RuH(PPh^3)を触媒とし、メチルビニルケトンへのα-シアノエステルのマイケル付加反応を検討した。高い触媒活性を示したが、不斉誘導は見られなかった。この原因として、触媒の原料として(Cp-P)RuCl(PPh^3)のジアステレオマ-混合物を用いたこと、及び不斉点が反応点から離れていることなどが考えられる。 そこで次に、不斉点をより反応点の近傍に持ってくることを目的とし、アルキル鎖でキレートしたCp-P配位子を利用して金属中心上に不斉点を有する遷移金属錯体の合成を検討した。インデニル環を有し単純なアルキル鎖でキレートされたCp-P配位子のロジウムカルボニル錯体にハロゲン化アルキルを反応させるとロジウム(III)アシル錯体が得られた。このアシル錯体には、面不斉とロジウム周りの中心性不斉によるジアステレオマ-が存在する。ハロゲン化アルキルとしてヨウ化エチルを用いると、一方のジアステレオマ-がほぼ選択的に得られた。また、反応性、および立体選択性がCp-P配位子の性質の違いにより大きく変化することがわかった。キレート鎖の短いもの、および、リン上の置換基がシクロヘキシル基より塩基性の低いフニル基を有するCp-P配位子を用いた方が高い反応性を示した。また、立体選択性はリン上の置換基にはあまり影響されず、キレート鎖の長い方が高くなる傾向があった。今後、ジアステレオマ-の分割を行い、金属上に不斉点を有するステニウム錯体を合成する。, kaken
  • Grant-in-Aid for General Scientific Research (B), 1994, 1995, 06455012, STUDIES ON TRANSITION METAL COMPLEXES WITH HYBRID CHELATE LIGANDS, TANI Kazuhide; YAMAGATA Tsuneaki; KATAOKA Yasutaka, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Osaka University, 5200000, 5200000, Transition metal complexes with a P-N,Cp-P,or N-C hybrid chelate ligand were synthesized and their structure and reactivity were examined. (1) As a new type of P-N hybrid chelate ligand, Ph_2-o-C_6H_4CH_2O(CH_2)_n-2-C_5H_3N(n=1,2,3) were prepared and their Pd and Pt complexes were prepared. By adjusting the chelate length cis-or trans-PdCl_2(PN) complexes were selectively obtained. The trans-PdCl_2(PN) is the first example of the transition metal complexes with a bidentatetrans cheate P-N ligand. The Pd(I) complex with the shortest Pd-Pd bond was prepared. Cationic Pt complexes having phosphine ligands were found to be active catalysts for stereoselective addition of alcohol to alkynes to give vinyl ethers or ketones. sigma-Vinyl Pd and Pt complexes having a P-O-N or a P-O-P tridentate ligand were isolated as the reaction intermediate and the reaction pathway was clarified. (2) Optically active Cp-P hybrid ligands connecting a cyclopentadienyl or an indenyl group with PPh_2 by a L-threitol backbone were prepared and their Ru and Rh complexes were prepared. It was found that the Ru complex was an effective catalyst for an asymmetric C-C bond forming reaction from terminal acetylene and allylic alcohol. As achiral Cp-P ligands general synthetic method of CpH(CH_2)_nPPh_2(Cp=C_5H_4 or 1-C_9H_6 ; n=2,3,4) was established and their transition metal chemistry was examined. Stereoselective addition of ethyl iodide to RhCl(CO)(Cp-P)[Cp=1-indenyl] to give one of the two diastereomeric acyl complexes has been achieved. By application of this reaction we will try to prepare a new optically active Cp-P complex having a chiral metal center. (3) A stereoselectve reaction between a Pd complex having an optically active C-N chelate ligand with a racemic phosphole derivative was studied., kaken
  • 重点領域研究, 1994, 1994, 06225222, 新規光学活性シクロペンタジエニル錯体の合成と不斉触媒反応への応用, 谷 一英; 山県 恒明; 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 2000000, 2000000, 我々は新しいタイプの光学活性配位子として、シクロペンタジエニル基(Cp)とヘテロ原子(L)がキレートされた光学活性二座配位子(Cp-P配位子)を開発し、このCp-P配位子を有する遷移金属錯体の合成と不斉触媒反応への応用を検討している。昨年、Cp-P配位子およびそのロジウム錯体の合成を報告した。今回、Cp-P配位子を有するルテニウム錯体を合成し、それをアセチレン化合物とアリルアルコールの不斉カップリング反応に応用した。 1、Cp-P配位子を有する光学活性ルテニウム錯体の合成 光学活性Cp-P配位子とRuCl_2(PPh_3)_3を反応させルテニウム錯体1を合成した。得られた錯体は、ルテニウム回りの絶対配置の違いによる2種(59:41)のジアステレオマ-混合物であった。 2、Cp-P配位子を有するルテニウム錯体の不斉触媒反応への応用 カチオン性ルテニウム錯体触媒によるアセチレン化合物とアリルアルコールのカップリング反応に、今回合成したCp-p配位子を有するルテニウム錯体1(ジアステレオマ-混合物)を応用した。末端アセチレンとアリルアルコールの混合物に対し、ルテニウム錯体1とNH_4PF_6から調整したカチオン性ルテニウム錯体を作用させると、光学活性ケトン2が得られた。この時、副生成物として、γ,δ-不飽和ケトン3の異性体混合物が生成した。反応の詳細及び2の光学収率に関しては現在検討中である。, kaken
  • 奨励研究(A), 1993, 1993, 05855136, 新規複合配位子を有する遷移金属錯体を用いた不斉触媒反応の開拓., 片岡 靖隆, 日本学術振興会, 科学研究費助成事業, 大阪大学, 800000, 800000, 本研究は不斉触媒反応への応用を目指し、シクロペンタジエニル誘導体(Cp)とホスフィノ基(P)がキレートされた配位子(Cp-P配位子)を設計し、その遷移金属錯体の合成を目的とした。今回まず、アキラルな炭素鎖でキレートされたCp-P配位子(1)と、光学活性Cp-P配位子(2)の一般的な合成法を確立した。これらのCp-P配位子のリチウム塩[Rh(CO)_2Cl]_2を反応させCp-P配位子を有する単核のロジウム錯体(3)を合成した。シクロペンタジエニル誘導体としてインデニル基を有するCp-P配位子(2b)を用いると、光学活性ロジウム錯体(4a)が黄色結晶性粉末として高収率で得られた。しかし、この錯体はインデン環の配向の違いによるジアステレオマ-の混合物で、現在その分離には成功していない。シクロペンタジエニル基を有するCp-P配位子(1a,2a)を用いると、生成するロジウム錯体は不安定なため収率よく単離することはできなかった。また、これらのロジウム錯体に光を照射すると、配位していた一酸化炭素が解離することを確認した。これを利用すると不斉触媒反応の開発が可能である。RuCl_2(PPh_3)_3を用いると同様の方法により単核のルテニウム錯体(5)を合成することができた。ルテニウムの場合は、どのCp-P配位子(1、2)を用いてもルテニウム錯体を単離することができた。, kaken
  • 重点領域研究, 1993, 1993, 05234217, 新規光学活性シクロペンタジエニル錯体の合成と不斉触媒反応への応用, 谷 一英; 片岡 靖隆; 巽 和行, 日本学術振興会, 科学研究費助成事業, 大阪大学, 2400000, 2400000, 本研究は新規光学活性キレートハイブリッド配位子の開発とその不斉触媒反応への応用を目的とした。そのため先ず、アキラルな配位子としてシクロペンタジエニル基(Cp)とホスフィノ基(PR_2)を種々の長さのメチレン鎖で結合したCp-P配位子1a-cの合成法を確立し、ついで光学活性Cp-P配位子として2種の光学活性骨格を有する2a-b,3を合成した。これらのCp-P配位子はいづれも空気に不安定な無色オイルとして得られ、スペクトル及び分析で同定した。合成したCp-P配位子と[Rh(CO)_2Cl]_2の反応で4,5などのいくつかの単核ロジウム錯体を合成し、スペクトルで同定した。シクロペンタジエニル誘導体としてインデニル基を用いると光学活性錯体5が黄色結晶性粉末として高収率で得られたが、インデン環の配向の違いによるジアステレオマー混合物が得られ、現在その分離には成功していない。, kaken
  • Grant-in-Aid for Scientific Research (C), 2008, 2010, 20550097, Development of Molecular Catalysts Having a Dockable Part for Asymmetric Bond Activations, KATAOKA Yasutaka, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Nara Women's University, 4810000, 3700000, 1110000, In order to develop novel molecular catalysts for reaction systems created by combining two organic reactions, asymmetric transformations and bond activations, we have designed the Ind-PO ligand, in which the indenyl group and the phosphine oxide group are connected by alkylene chains, and the Ind-NHC ligand, in which the indenyl group and the N-heterocyclicarben part are connected by an ethylene chain, and prepared their iridium complexes having several chiralities such as the planar chirality on the indenyl ring and a metal-centered chirality. We also demonstrated their reactivity for intramolecular C-H bond activations and catalytic activities for asymmetric allylations., kaken


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