Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/acsomega.2c03496

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

<p>Improved performance of an IrO₂ nanoparticle catalyst because of the B–N, B–C, and N–C functional groups and conductive rGO network in BN-rGO.</p>

DOI： 10.1039/d1ta00158b

Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/acs.energyfuels.9b00994

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley Blackwell  

Palladium nanoparticles supported on 5 %-nitrogen-doped, herringbone-type carbon nanofibers (Pd/N-CNF-H), which are prepared by thermally decomposing [Pd2(dba)3⋅CHCl3] (dba=dibenzylideneacetone) in toluene in the presence of N-CNF-H, were found to be an efficient catalyst for the chemoselective hydrogenation of alkenyl and nitro moieties in benzyl-protected alcohols and carboxylic acid derivatives with high turnover frequencies: the hydrogenation reactions of these functional groups proceeded smoothly even at ambient temperature under atmospheric H2 pressure, and the benzyl protecting groups in the molecules remained intact. Moreover, the recovered Pd/N-CNF-H catalyst could be reused without loss of its catalytic activity or chemoselectivity. The Pd/N-CNF-H catalyst also acted as an effective hydrogenation catalyst for the reduction of aromatic ketones to the corresponding benzyl alcohol derivatives with good to high product selectivity.

DOI： 10.1002/cctc.201701326

Authorship：Lead author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：THE CARBON SOCIETY OF JAPAN  

The easy synthesis of transition metal nanoparticles supported on three types of carbon nanofibers (platelet: CNF-P, tubular: CNF-T, herringbone: CNF-H) and nitrogen-doped CNF-H (N-CNF-H) is accomplished by pyrolysis of metal carbonyl clusters such as Ru₃(CO)₁₂, Rh₄(CO)₁₂, and Ir₄(CO)₁₂, and alkene complexes such as Pd₂(dba)₃·CHCl₃ and Pt(dba)₂ [dba: dibenzylideneacetone]. Transmission electron microscopy of these CNFs with immobilized metal nanoparticles (M/CNFs and M/N-CNF-H) showed that metal nanoparticles whose size could be controlled, existed on the CNFs, and that their location was dependent on the surface nanostructure of the CNFs: on the edge of the graphite layers (CNF-P), in the tubes and on the surface (CNF-T), and between the layers and on the edge (CNF-H). Among these M/CNFs, Ru/CNF-P and Rh/CNF-T showed excellent catalytic activity towards arene hydrogenation with high reusability and functional group tolerance, while the Pt/CNF-P behaves as an efficient catalyst for the hydrogenation of substituted nitroarenes to the corresponding aniline derivatives with the other functional groups remaining intact. Pt and Pd nanoparticles supported on N-CNF-H act as poisoning catalysts for the transformation of internal alkynes to (Z)-alkenes over Pd/N-CNF-H, and for the transformation of nitroarenes to the corresponding anilines and N-hydroxylamines over Pt/N-CNF-H.

DOI： 10.7209/tanso.2015.35

Other Link： https://jlc.jst.go.jp/DN/JLC/20005126468?from=CiNii

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The appropriate design of a ligand (L) in IrCl(CO)(L)(2) (4) realized the efficient synthesis of pi-conjugated enamines possessing hole-transport properties. The iridium complex with electron-withdrawing phosphorus ligands catalyzed the hydrosilylation of amides to the corresponding silylhemiaminals, which were transformed to the enamines by heat or by treatment with acids. High catalytic efficiency (TON &gt; 10,000) was achieved, which made it possible for the residual iridium in the enamine product to be below 20 ppb.

DOI： 10.1021/acs.organomet.5b00636

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

The reaction of three types of carbon nanofibers (CNFs; platelet: CNF-P, tubular: CNF-T, herringbone: CNF-H) with Ir-4(CO)(12) in mesitylene at 165 degrees C provided the corresponding CNF-supported iridium nanoparticles, Ir/CNFs (Ir content=2.3-2.6wt.%). Transmission electron microscopy (TEM) studies of these Ir/CNF samples revealed that size-controlled Ir nanoparticles (average particle size of 1.1-1.5 nm) existed on the CNFs. Among the three Ir/CNF samples, Ir/CNF-T showed an excellent catalytic activity and chemoselectivity towards hydrogenation of functionalized nitroarenes and imines; the corresponding aniline derivatives were obtained with high turnover numbers at ambient temperature under 10atm of H-2, and the catalyst is reusable. Ir/CNF-T was also effective for the reductive N-alkylation of anilines with carbonyl compounds.

DOI： 10.1002/asia.201301184

Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC RHEOLOGY, JAPAN  

Solid-like and liquid-like viscoelastic behaviors at low and high temperature, T, respectively, observed for carboxylterminated telechelic poly(ethyrene-butylene) (CTPEB) neutralized with octadecylamine ODA prepared by melt mixing are studied in relation with the structure examined by XRD, FT-IR, DSC and small angle neutron scattering. When the mole ratio of -NH2 and -COOH, NH2/COOH in CTPEB/ODA is 1.4 or higher, CTPEB/ODA was solid-like at 298K, while it was liquid-like having almost the same viscosity as CTPEB at 343K. The network structure formed at low T was easily fractured by small strain and cannot be reformed at low T. However, when the sample is annealed at 353K, cooled and kept for a few hours at T &lt; 300K, the solid-like behavior is reproduced. It was concluded that the network formation at low T and its disappearance at high T for CTPEB/ODA is caused by non-crystalline association/dissociation of C18 residues in ODA connected to CTPEB by ionic bond (NH3+COO-). Due to the small M(w)of CTPEB, only longer chains (similar to 1/3 of total chains) connected to ODA aggregates form network structure and sustain the constant G' in this system at low T.

DOI： 10.1678/rheology.42.33

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/cctc.201200058

Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Novel transformation of carboxylic acids to aldehydes is achieved by a one-pot procedure consisting of a ruthenium-catalyzed hydrosilane reduction with 1,2-bis(dimethylsilyl)benzene (2) followed by hydrolysis of the resulting cyclic disilylacetals 4.

DOI： 10.1246/cl.2012.229

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

A triruthenium cluster, (mu(3), eta(2), eta(3), eta(5)-acenaphthylene)Ru-3(CO)(7) effectively catalyzes primary-alkylation reaction of electron-rich aromatic rings using a combination of hydrosilane and ester as a source of the primary-alkyl group. The reaction involves electrophilic substitution of arenes by carbocationic species stabilized by a neighboring alkoxy or siloxy group generated during the reduction of esters giving alkylated arenes after reductive removal of the alkoxy or siloxy group at the benzylic position. (C) 2011 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2011.08.033

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

DOI： 10.1002/cctc.201100135

Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

The H-shape alkanes of various arm lengths have been synthesized successfully through the Grignard reaction. The detailed investigation of these novel compounds may allow us to widen the topological chemistry field furthermore. The molecular form and molecular packing structure in the crystal lattice have been revealed successfully on the basis of X-ray structure analysis as well as the analysis of Raman longitudinal acoustic modes (LAM) sensitive to the alkyl zigzag chain segments. The molecular conformation in the crystal lattice is deformed markedly from the originally imagined H-shape. In the cases of C3HOH to C6HOH, for example, the molecules are packed in a complicated manner and the OH⋯O hydrogen bonds govern the whole intermolecular interactions mainly. Since the alkyl segmental length is not very long, the conformational change is not very drastic, i.e., the small configurational entropy. Synergic effect of the hydrogen bonds and the small configurational entropy gives the higher melting point as known from the thermal data. On the other hand, in the cases of C10HOH and C12HOH, one of the long alkyl chain arms is found to be bent by 90° so that all of the alky chain segments of planar-zigzag conformation can be packed as closely as possible, and the intermolecular OH⋯O hydrogen bonds are also formed effectively without any mistake. As a result, the contribution of nonbonded intra- and intermolecular van der Waals interactions between the trans-zigzag alkyl chain segments become major, and the coupling of this enthalpy effect with the larger configurational entropy effect of the molecular shape results in the decrement of the melting point which approaches gradually that of longer n-alkane compound. In this way a sensitive balance between the nonbonded van der Waals interact ons, the OH⋯O hydrogen bonds, as well as the configurational entropy effect gives the characteristic thermal behavior of the H-shape compounds. The thus-newly synthesized H-shape alkane compounds should give us new insight into the packing topology of complicated molecules, leading to the development of new functionality unexpected for normal linear alkane compounds. © 2011 American Chemical Society.

DOI： 10.1021/jp200782f

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

DOI： 10.3390/molecules16075387

Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/bcsj.20100155

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/asia.201000527

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Hydrosilanes act as a reagent to cleave the C-O bond of OtBu groups in carbamates, carbonates, esters, and ethers by catalysis of a triruthenium cluster. The reaction offers a novel deprotection method for OtBu groups under neutral conditions, showing unique selectivities that have never been accomplished with conventional Bronsted or Lewis acidic promoters. Possible mechanisms for C-O cleavage are discussed oil the basis of NMR spectroscopic analysis.

DOI： 10.1002/ejoc.200901279

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Novel polysiloxane gel, in which CuCl/bipyridine species are immobilized, is prepared by treatment of polymethylhydrosiloxane with 4,4&apos;-bis[(2-propenyl)oxy]-2,2&apos;-bipyridine and 1,5-hexadine in the presence of Karstedt&apos;s catalyst followed by addition of CuCl. This polysiloxane gel acts as a reusable catalyst in the atom-transfer radical cyclization of alpha-halogenated acetamide derivatives in high turnover numbers without allowing leakage of the metal species.

DOI： 10.1039/b923213c

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Rhodium nanoparticles supported on a carbon nanofiber (Rh/CNF-T) show high catalytic activity toward arene hydrogenation under mild conditions in high turnover numbers without leaching the Rh species; the reaction is highly tolerant to epoxido groups, which often undergo ring-opening hydrogenation with conventional catalysts.

DOI： 10.1021/ol902018g

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions The rate of the reaction is dependent on the distance of two Si-H groups, 1,1,3,3-tetramethyidisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO(2), CO(2)R, CN, C=C, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.

DOI： 10.1021/ja9055307

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Novel polysiloxane gels, to which platinum species are encapsulated, are prepared by treatment of polymethylhydrosiloxane with alkenes in the presence of Karstedt&apos;s catalyst. These gels act as reusable catalysts in the reduction of functionalized nitroarenes with H(2) to the corresponding substituted anilines without leaking the catalyst species.

DOI： 10.1021/ol9001366

Language：Japanese   Publishing type：Research paper (scientific journal)  

We synthesized a complex branched alkane (H-shaped) with two hydroxyl groups attached to branching points and studied its crystalline structure and also compatibility with high density polyethylene (PE). Results of DSC and X-ray diffraction on solution-crystallized and bulk-crystallized H-shaped alkanes gave same lattice constants for a triclinic type of crystal, a = 1.04nm, b = 1.27nm, c = 1.60nm, α = 95.7°, β = 91.6°, and γ= 109.4°. H-shaped/PE binary system showed a solid solution region 0.05 &lt
Φ H &lt
0.40, where Φ H is the volume fraction of H-shaped alkane. On the other hand, in the region 0.46 &lt
Φ H &lt
0.90, H-shaped and PE are considered to mix athermally in the liquid state and to present separately in this binary system, taking crystal structures different from each other. © 2009 The Society of Materials Science.

DOI： 10.2472/jsms.58.1

Authorship：Lead author,　Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Society of Synthetic Organic Chemistry  

Facile synthesis of ruthenium, palladium and platinum nanoparticles supported on three types of carbon nanofibers (platelet: CNF-P, tubular. CNF-T, herringbone: CNF-H) is accomplished by pyrolysis of ruthenium carbonyl clusters, and pyrolysis and hydrogenolysis of Pd2(dba)3-CHC1 3 and Pt(dba)2 [dba: dibenzylideneacetone). TEM studies of these M/CNFs revealed that size-controlled metal nanoparticles existed on the CNFs, and that of the location was dependent on the surface nanostructures of CNFs: On the edge of the graphite layers (CNF-P), in the tubes and on the surface (CNF-T), and between the layers and on the edge (CNF-H). Among these M/CNFs, the Ru/CNF-P showed excellent catalytic activity towards arene hydrogenation with high reusability and functional group tolerance. The present Ru system is applicable to the production of octahydro-l,l'-binaphthyls by partial hydrogenation of l,l'-binaphthyls. While the Pt/CNF-P behaves as an efficient catalyst for hydrogenation of substituted nitroarenes to the corresponding aniline derivatives with other functional groups remaining intact.

DOI： 10.5059/yukigoseikyokaishi.67.724

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200905025

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

The combination of IrCl(CO)(PPh(3))(2) with 1,1,3,3-tetramethyldisiloxane or poly(methylhydrosiloxane) (PMHS) is found to be an efficient catalyst system for the preparation of aldenamines from carboxamides; in particular, facile removal of silicone and iridium residues from the product can be achieved by the use of PMHS.

DOI： 10.1039/b821317h

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/ejoc.200800523

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Platinum and palladium nanoparticles supported on three types of carbon nanofibers (CNFs) are synthesized and used as catalysts in the hydrogenation of nitroarenes. Nanosized platinum particles dispersed on platelet-type CNF efficiently catalyze the reduction of functionalized nitroarenes to the corresponding substituted anilines in high turnover numbers with other functional groups remaining intact.

DOI： 10.1021/ol800277a

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Novel ruthenium-encapsulating polysiloxane gels are prepared by treatment of polymethylhydrosiloxane with diols in the presence of (mu(3),eta(2),eta(3),eta(5)-acenaphthylene)Ru(3)(CO)(7), and act as reusable catalysts in the isomerization of alkenes without leakage of the catalyst species.

DOI： 10.1039/b809937e

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

[GRAPHICS]
Use of Ru/CNF-P, nanoruthenium particles dispersed on a nanocarbon fiber support, realizes highly efficient catalytic partial hydrogenation of 1,1'-bi-2-naphthol and -naphthylamine derivatives. The reactions proceed in high turnover numbers without racemization of the axial chirality, offering a practical procedure for the production of optically pure 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyls in good to high yields.

DOI： 10.1021/jo702015j

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

The addition of amines eliminates the catalytic activity of a triruthenium cluster in the hydrosilane reduction of ketones and esters without affecting the rate of reduction of amides; selective reduction of the amide group in amido ketones and amido esters is accomplished.

DOI： 10.1039/b711743d

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

[GRAPHICS]
A trituthenium cluster, (mu(3),eta(2),eta(3),eta(5)-acenaphthylene)Ru-3(CO)(7) (1) catalyzes the reaction of secondary amides with hydrosilanes, yielding a mixture of secondary amines, tertiary amines, and silyl enamines. Production of secondary amines with complete selectivity is achieved by the use of higher concentration of the catalyst (3 mol %) and the use of bifunctional hydrosilanes such as 1, 1,3,3-tetramethyldisiloxane. Acidic workup of the reaction mixture affords the corresponding ammonium salts, which can be treated with a base, providing a facile method for isolation of secondary amines with high purity. In contrast, tertiary amines are formed with high selectivity by using lower concentration of the catalyst (I mol %) and polymeric hydrosiloxanes (PMHS) as reducing agent. Reduction with PMHS encapsulates the ruthenium catalyst and organic byproducts to the insoluble silicone resin. The two reaction manifolds are applicable to various secondary amides and are practical in that the procedures provide the desired secondary or tertiary amine as a single product. The product contaminated with only minimal amounts of ruthenium and silicon residues. On the basis of the products and observed side products as well as NMR studies a mechanistic scenario for the reaction is also described.

DOI： 10.1021/jo070591c

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Bis(oxazolinyl)phenyl-palladiui-n(II)(Phebox-Pd) complexes were found to be efficient catalysts for Suzuki-Miyaura coupling reactions of aryl boronic acids and their derivatives with aryl halides to give the corresponding biaryl products in high yield along with moderate enantioslectivities in the case of axially chiral induction. The catalytic activity was attained more than 900,000 of TON and 45,000 of TOF. The catalyst can be recovered quantitatively and could be reused for Suzuki-Miyaura reactions. (c) 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2007.03.063

Other Link： http://orcid.org/0000-0001-6368-4823

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

The reaction of three types of carbon nanofibers (CNFs; platelet: CNF-P, tubular: CNF-T, herringbone: CNF-H) with [Ru-3(CO)(12)] in toluene heated at reflux provided the corresponding CNF-supported ruthenium nanoparticles, Ru/CNFs (Ru content= 1.1-3.8wt%). TEM studies of these Ru/CNFs revealed that size-controlled Ru nanoparticles (2-4 nm) exist on the CNFs, and that their location was dependent on the surface nanostructures of the CNFs: on the edge of the graphite layers (CNF-P), in the tubes and on the surface (CNF-T), and between the layers and on the edge (CNF-H). Among these Ru/CNFs, Ru/CNF-P showed excellent catalytic activity towards hydrogenation of toluene with high reproducibility; the reaction proceeded without leaching of the Ru species, and the catalyst was reusable. The total turnover number of the five recycling experiments for toluene hydrogenation reached over 180000 (mol toluene) (mol Ru)(-1). Ru/CNF-P was also effective for the hydrogenation of functionalized benzene derivatives and pyridine. Hydrogenolysis of benzylic C-O and C-N bonds has not yet been observed. Use of poly(ethylene glycol)s (PEGs) as a solvent made possible the biphasic catalytic hydrogenation of toluene. After the reaction, the methylcyclohexane formed was separated by decantation without contamination of the ruthenium species and PEG. The insoluble PEG phase containing all of the Ru/CNF was recoverable and reusable as the catalyst without loss of activity.

DOI： 10.1002/asia.200700175

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

DOI： 10.1039/b617356j

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Facile synthesis of ruthenium nanoparticles supported on the carbon nanotibers (CNFs) is accomplished by thermal decomposition of Ru-3 (CO)(12); ruthenium species on the platelet-type CNF are dispersed homogeneously and selectively on the edge of the graphite layers with narrow size distributions and behaves as an excellent catalyst for arene hydrogenation.

DOI： 10.1246/cl.2006.876

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.tetlet.2006.06.165

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Chiral palladium and platinum complexes bearing non-symmetrical, PCN pincer ligand, 6-methoxy-3-(4'-isopropyl-2'-oxazolin-2'-yl)phenyl diphenylphosphinite [i-Pr-Phemox-OPPh2], are first synthesized via oxidative addition of (i-Pr-Phemox-OPPh2)Br 6 to Pd-2(dba)(3)(.)(CHCl3) or Pt(dba)(2) and subsequent treatment with silver salts. (c) 2005 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ica.2005.06.034

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Treatment of lithium phosphinoamides, Ph2PN(Li)R [R = Bu-1, Pr-i], with TiCl4 results in formation of titanium phosphinoamides, (Ph2PNR)(2)TiCl2 [R = Bu-t (1a), Pr-i (1b)]. Crystallographic studies show that there are covalent bonds between the titanium and two nitrogen atoms, whereas two phosphorus atoms are coordinated to the metal center intramolecularly. Variable-temperature NMR studies suggest reversible dissociation of the phosphorus moieties from the titanium in solution. The dissociated phosphorus moieties are effectively captured by Pt(11) species; reactions of la with either (eta(4)-COD)PtCl2, (eta(4)-COD)Pt(R)(Cl) (R = Me, p-Tol), or [Me2Pt(mu-SMe2)](2) afford the corresponding Ti-Pt heterobi metallic complexes. The molecular structures of these complexes reveal that they have a six-membered dimetallacycle, in which a titanium and a platinum are connected by two bridging phosphinoamide ligands; the Pt-Ti distances indicate the existence of a Pt -&gt; Ti dative bond. The conformation of the dimetallacycle is a boat form, with two metals at the bow and the stem in the crystal; however, dynamic conformational change involving cleavage and re-formation of the Pt-Ti dative bond is indicated from variable-temperature NMR studies.

DOI： 10.1021/om0509600

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Atom-transfer radical cyclization (ATRC) catalyzed by coordinatively unsaturated ruthenium alkoxides 4, [(eta(5)-C5Me5)-Ru(OR)](2), is investigated, and ruthenium methoxide 4a (R=Me) is found to exhibit excellent catalytic activity for the cyclization of N-allyl-alpha,alpha-dichloroacetamides at ambient temperature. Addition of some amounts of two-electron donor ligands such as pyridine and triphenylphosphine improves the catalyst efficiency to afford the corresponding gamma-lactams in high yields. The high catalytic activity of this catalyst system enables to control the diastereoselectivity of this 5-exo cyclization kinetically. The present 4a/pyridine system is also effective for the 4-exo cyclization of N-vinylacetarnides to afford the corresponding beta-lactams in quantitative yields. The 4a/pyridine system is also active towards the ATRP of methyl methacrylate (MMA) at room temperature to afford the poly(MMA) with narrow molecular weight distributions (M-w/M-n = 1.2) at the initial stage. (c) 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2006.01.011

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.tet.2005.08.037

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

DOI： 10.1021/ja0544531

Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/om050091e

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.jorganchem.2004.09.075

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

DOI： 10.1039/b502942b

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley Blackwell  

DOI： 10.15227/orgsyn.082.0188

Language：English   Publishing type：Research paper (scientific journal)  

The polymerization of vinyl ethers (CH2=CHOR, R = nBu, iBu, tBu, iPr) is catalyzed by a ruthenium cluster, (μ3,η2:η3: η5-acenaphthylene)Ru3(CO)7 (1), using several hydrosilanes as the initiator to give polyvinyl ethers with M n = 2000-25 000 and Mw/Mn = 1.2-3.4. Spectroscopic analysis of the polymer reveals the existence of an organosilyl moiety at the end group, which is supported by UV and RI detection of GPC. The poly(tert-butyl vinyl ether) prepared by PhMe2SiD as the initiator contains a -CDHOtBu group at the other polymer end. These data suggest the polymer structure is R3Si-(CH2CHOR) n-H. Dominant heterotacticity was observed for the polymer structure, which was independent of organosilanes or solvents.

DOI： 10.1021/om049499m

Language：English   Publishing type：Research paper (scientific journal)  

Isocyanide complexes of nickel, NiBr2(CNAr)2, are found to be active catalysts for polymerization of ethylene in the presence of methylaluminoxane (MAO). The catalytic activity and properties of polyethylene formed vary with substituents on the aryl group, in particular, at the 2- or 2,6-positions. The nickel complexes having 2,6-diphenylphenyliso-cyanide and its analogues are catalysts showing moderate activity and giving high molecular weight polyethylene (Mv > 106), whereas those bearing 2-phenylphenylisocyanide and its analogues give polyethylene with Mw = 103-104.

DOI： 10.1021/om0498394

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Georg Thieme Verlag KG  

DOI： 10.1055/s-2003-41474

Authorship：Lead author,　Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Society of Synthetic Organic Chemistry  

Optically active bis(oxazolinyl)phenyl (Phebox) was designed as an anionic N-C-N pincer ligand, and (Phebox) SnMe3 was prepared as its stable precursor. The aqua complexes, (Phebox)RhIIIX2(H2O) [X = Cl, Br, F], [(Phebox)MII(H2O)] (BF4) [M = Pd, Pt] and [(Phebox)PtIV (H2O)] (BF4), were synthesized by the oxidative addition or transmetallation of RhI, PdII and PtII precursors with (Phebox)SnMe3 and subsequent ligand exchange reaction. X-ray structure studies revealed that the octahedral structure of RhIII complex is isosteric with the PtIV, and the PdII and PtII complexes are almost the same configuration with a square-planar structure. These aqua complexes acted as efficient catalysts for enantioselective allylation of aldehydes with allyltin reagents, hetero Diels-Alder reaction of Danishefsky's diene with glyoxylates and the aldol-type condensation of tosylmethyl isocyanide with aldehydes. While (Phebox)RhIII(SnMe3Cl complexes catalyzed the Michael addition of α-cyanopropionates to acrolein.

DOI： 10.5059/yukigoseikyokaishi.61.343

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/1521-3765(20020703)8:13<2968::aid-chem2968>3.0.co;2-6

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/om020274q

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/om011011j

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/om010018y

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/s0040-4020(00)01049-8

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/om9908682

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Asymmetric reaction of an excess of trans-cyclooctene (1) with chiral bis(dihydrooxazolyl)pyridineruthenium (pybox-ip, 3) complex selectively gives the corresponding ruthenium complex 4R, [RuCl2(pybox-ip){(R)-trans-cyclooctene}], and (S)-trans-cyclooctene 2S. The X-ray crystal structure of complex 4R shows a C25-C18-C19-C20 dihedral angle of 125 degrees with a C18-C19 bond length of 1.41 Angstrom. Complex 4R can also be obtained by UV irradiation of a solution of cis-cyclooctene and [RuCl2-(pybox-ip)(C2H4)] (8) in THF in the presence of a photosensitizer. Even in the absence of the photosensitizer, 4R is produced by irradiation in the presence of cis-cyclooctene. The photoreaction has been applied to cis-cycloheptene to give a 1:1 mixture of the diastereomeric complexes of [Ru(pybox-ip)-{trans-cycloheptene}].

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/om990251k

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

The reaction of (Phebox)SnMe3 1 [PheboxH = 2,6-bis(oxazolinyl)benzene] and [(c-octene)RhCl](2) in the presence of CCl4 provided air-stable and water-tolerant (Phebox)RhCl2(H2O) complexes 2 which acted as asymmetric catalysts for the enantioselective allylation of aldehydes in up to 80% ee.

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Single-chiral bis(oxazolinyl)pyridine ligands were examined as ligands for ruthenium-catalyzed asymmetric catalytic cyclopropanation of olefins: enantioselectivities up to 94% for the trans-cyclopropane were observed. (C) 1998 Elsevier Science Ltd. All rights reserved.

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The reaction of [(p-cymene)RuCl2](2) and 2,6-bis(oxazolin-2-yl)pyridines (PYbox) in the presence of alpha,beta-unsaturated carbonyl compounds as prochiral olefins gave eta(2)-olefin complexes as single conformations. From its NMR spectra and X-ray diffraction, these chiral (Pybox)RuCl2 fragments not only discriminated the one enantioface (si-face) of the alkenes but also fixed the conformation of carbonyl moiettes s-trans.

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Ruthenium-pyridine-2,6-dicarboxylate (pydic) complexes 1-3 of terpyridine and chiral bis(oxazolinyl)pyridines (pybox-ip and pybox-ph), which can be synthesized from [Ru(p-cymene)Cl-2](2) and the corresponding ligands, exhibit catalytic activity for epoxidation of trans-stilbene in combination with [bis(acetoxy)iodo]benzene: asymmetric induction with 2 was observed in 74% ee for trans-stilbene.

Language：English   Publishing type：Research paper (scientific journal)  

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)  

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The transmetalation of Phebox-ip-SnMe3 [Phebox = 2,6-bis(oxazolinyl)phenyl] 1c with RhCl3(H2O)(3) and PdCl2(PhCN)(2) gave (Phebox-ip)RhCl2(H2O) 2a and (Phebox-ip)PdCl 3 under mild conditions in 45% and 96% yields, respectively. The crystal structures of (Phebox-ip)Rh Cl-2(t-BuNC) 2b, which was obtained by the reaction of 2a with t-BuNC, and 3 have bees determined by X-ray diffraction.

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The reaction of RuCl2(pybox)(C2H4) [pybox = 2,6-bis(oxazolinyl)pyridine] 1 and OsCl2(pybox)(propylene) 6 with dimethyl diazomalonate gave stable dicarbonylcarbene complexes 9 and 10 in 92% and 59% yields, respectively. The carbene moiety of 9 proved to be almost parallel in the Cl-Ru-Cl plane by 10-12 degrees and perpendicular to the pybox plane by X-ray analysis. The transfer of the carbene moiety of 9 to styrene could be observed at 110 degrees C to give the corresponding cyclopropane 15 but in a low yield (11%) with asymmetric induction in 36% ee.

Language：English   Publishing type：Research paper (scientific journal)  

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)  

A chiral titanium complex 1a derived from 6,6'-dibromo-1,1'-bi-2-naphthol is found to give higher endo- and enantioselectivity along with higher catalytic activity than the parent binaphthol-derived titanium complex 1b in the (hetero) Diels-Alder reactions of 1-methoxydienes (2a and 2c) with methacrolein and glyoxylate but not with bromoacrolein.

DOI： 10.1055/s-1995-5138

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Diastereo- and enantioselective carbonyl-ene reaction of glyoxylate (2) with trisubstituted olefins (3) catalyzed by chiral titanium complexes (1a), derived from 6,6′-dibromo-1,1′-bi-2-naphthol and diisopropoxytitanium dihalides, is found to provide syn-diastereomers exclusively along with a high level of enantioselectivity. © 1994.

DOI： 10.1016/S0040-4039(00)73470-8

Language：English   Publishing type：Research paper (scientific journal)  

A new type of titanium complex (N) derived from modified binaphthyl, 1,1′-bi-6-bromo-2-naphthol (6-Br-BINOL, 1) (98% e.e.) is found to be an extremely efficient asymmetric catalyst for the glyoxylate-ene reaction with α-methylstyrene to give the ene product with 97.5% e.e. in 94% yield. A certain level of positive non-linear effect (asymmetric amplification) is also observed in the present glyoxylate-ene reaction. The 6-Br-BINOL-derived titanium complex (98% e.e.) affords the glyoxylate-ene product of methylenecyclohexane with more than 99% e.e.! in 82% yield. Furthermore, 70% e.e. of 6-Br-BINOL leads eventually to 85% e.e. of the glyoxylate-ene product with α-methylstyrene. A higher level of asymmetric induction is observed in a less polar solvent, toluene, suggesting that dipolar repulsion is operative in controlling the conformation of the ligand 6-Br-BINOL (1). Unfortunately, however, the titanium complex N′ derived from the binaphthyl ligand 2 with the sterical demanding trifylamine moiety gave a disappointingly low level of asymmetric induction in the glyoxylate-ene reaction. © 1994.

DOI： 10.1016/0020-1693(94)03895-3

Language：English   Publishing type：Research paper (scientific journal)  

Asymmetric Diels-Alder (D.—A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the enrfo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at —20 °C. Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.—A. cycloaddition of methacrolein and glyoxylate with 1, 3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (J?)-l with (S>1 or (±)-l.© 1994, American Chemical Society. All rights reserved.

DOI： 10.1021/ja00086a014

Language：English   Publishing type：Research paper (scientific journal)  

Asymmetric Diels-Alder reactions of methacrolein and 1,4-naphthoquinone with 1,3-dienol derivatives catalyzed by the chiral binaphthol (BINOL)-derived titanium complex 1 are shown to provide the corresponding endo-adducts in high enantiomeric purity. The naphthoquinone adduct can serve as a synthetic intermediate of tetracycline antibiotics. © 1991.

DOI： 10.1016/S0957-4166(00)86118-2

Authorship：Lead author,　Corresponding author   Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)  

Authorship：Lead author,　Corresponding author   Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)  

Total pages：8 v. (6223 p.)   Language：English   Book type：Scholarly book

Presentation type：Oral presentation (invited, special)  

Presentation type：Oral presentation (invited, special)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Event date： 2018.11

Language：Japanese   Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (invited, special)  

Presentation type：Oral presentation (general)  

Presentation type：Oral presentation (general)