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

A highly regioselective and stereoselective difunctionalization reaction of 1,3-diene with amine and disilane to form C-N and C-Si bonds via a one-step Pd/Cu/O-2 system is disclosed. The difunctionalization reaction affords allylic silanes, including the allylic amine moiety, in up to 92 % yield in the absence of any acid, base, or external ligand. The developed synthetic methodology can be scaled to 100 g in high yield with high Z-selectivity, which demonstrates the feasibility of the reaction for industrial applications.

DOI： 10.1002/chem.202100043

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

DOI： 10.1246/bcsj.20200115

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Copyright © 2020 American Chemical Society. Herein, the synthesis of new N,N-dimethylformamide (DMF)-protected palladium nanoparticles (Pd NPs-OAc) employing Pd (OAc)2 (â• Pd(OCOCH3)2) as the NP precursor is reported. Pd NPs-OAc were comprehensively characterized by transmission electron microscopy, FT-IR, NMR, and X-ray photoelectron spectroscopy to determine the Pd NP size distribution and the coordination state of DMF. Pd NPs-OAc were compared with Pd NPs-Cl, using PdCl2 as the NP precursor. The Suzuki-Miyaura cross-coupling reaction proceeded efficiently in the presence of Pd NPs-OAc and a high catalytic activity was observed with a turnover number of up to 1.5 × 105. Furthermore, the Pd NP-OAc catalysts could be recycled at least five times.

DOI： 10.1021/acsomega.0c01006

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

N,N-Dimethylformamide-stabilised Pd nanocluster (NC) catalysed cross-coupling reactions of hydrosilane/disilane have been investigated. In this reaction, the coupling reaction proceeds without ligands with low catalyst loading. N,N-Dimethylacetamide is a crucial solvent in these reactions. The solvent effect was considered by various techniques, such as transmission electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Pd NCs can be recycled five times under both hydrosilane and disilane reaction conditions.

DOI： 10.1039/c9ra02895a

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

Ti Pd alloys were investigated as heterogeneous catalysts for hydrogen autotransfer reactions. This is the first reported study of alloys as catalysts for hydrogen-borrowing reactions using alcohols. We improved the catalytic activities of alloys by increasing their specific surface areas via a hydrogenation powdering process. The reactivities and selectivities of hydrogenated Ti Pd alloys [Ti Pd(Hy)] were higher than those of non-hydrogenated alloy catalysts in N-alkylation by hydrogen autotransfer using alcohols. A plausible catalytic cycle is proposed based on control studies and deuterium labelling experiments.

DOI： 10.1002/cctc.201900318

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

Ti-Pd alloys have been found to be novel heterogeneous palladium catalysts for organic cross-coupling reactions. Catalyst preactivation is not necessary, resulting in facile recovery and reuse of the catalysts. Palladium is not leached into the reaction solution and the catalysts can be recycled several times without losing their catalytic activity.

DOI： 10.1246/bcsj.20180363

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

Highly activated, monodispersed N,N-dimethylformamide (DMF)-stabilized iron-oxide nanoparticles (Fe2O3 NPs) were synthesized by using iron(III) acetylacetonate as a precursor under open-air conditions. The resulting Fe2O3 NPs were characterized by various techniques (e.g., transmission electron microscopy, dynamic light scattering, X-ray diffraction, X-ray photoelectron spectroscopy, FTIR spectroscopy, and X-ray adsorption near-edge structure). The Fe2O3 NPs exhibited efficient catalytic activity for the hydrosilylation of alkenes without the need for further additives. An effective recycling process of the colloidal catalyst by extraction with a hexane/DMF system was developed, and recycling of the catalyst over five cycles did not result in any significant loss in catalytic activity.

DOI： 10.1002/cctc.201800161

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：JAPAN INST METALS  

To identify the reasons why Ti-Pd alloys for hydrogen storage materials show good hydrogenation properties, X-ray photoelectron spectroscopy and the Suzuki-Miyaura cross-coupling reaction were used to investigate a small amount of Pd added Ti-Pd alloys. Pd in or on Ti oxide films is in a valence state of 0 (Pd-0). Catalytic activity was shown by Pd-0 in the Suzuki-Miyaura cross-coupling reaction. Therefore, the enhanced hydrogenation properties of Ti-Pd alloys for hydrogen storage materials is due to Pd-0's catalytic activity in dissociating hydrogen molecules. In addition, the potential catalytic activity of Ti-Pd alloys was shown to be based on a Pd catalyst.

DOI： 10.2320/matertrans.M2018240

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© 2018 The Royal Society of Chemistry. We show that N,N-dimethylformamide-stabilized Pd nanoclusters (NCs) have high catalytic activity in the reaction of substituted 2-iodoanilines with alkynes to give 2,3-disubstituted indoles. This indole synthesis does not require phosphine ligands and proceeds with low Pd catalyst loadings. The Pd NCs were separated from the mixture after the reaction, and recycled at least three times. Transmission electron microscopy images showed that the Pd particle size before the reaction was 1.5-2.5 nm. The particle size after the reaction was 2-3 nm. X-ray photoelectron spectroscopy showed that the binding energy of the Pd NCs before the reaction was 335.0 eV.

DOI： 10.1039/c8ra01410h

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

NbCl5-catalyzed [2 + 2 + 2] cycloaddition of nitriles with alkynes was used to synthesize pyrimidine derivatives. In this reaction, the use of individual Lewis acids, namely NbCl5 and FeCl3, is a key strategy for achieving the reaction using a catalytic amount of NbCl5. The roles of the two Lewis acids were investigated using FT-IR spectroscopy. The results showed that NbCl5 served as an efficient Lewis acid catalyst for nitrile activation, whereas FeCl3 showed stronger Lewis acidity toward pyrimidines, releasing NbCl5 into the catalytic cycle.

DOI： 10.1021/acs.orglett.7b02708

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

A NbCI5, Zn, and PCy3 catalytic system that generated low-valent Nb species is used for the synthesis of bicyclic cyclohexadienes from diynes and simple alkenes. A phosphine ligand, is important for stabilizing low-valent Nb in the cycloaddition. The bicyclic cyclohexadiene skeleton is important in transition-metal-catalyzed intramolecular cyclo-additions.

DOI： 10.1021/acs.orglett.7b02672

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：GEORG THIEME VERLAG KG  

We report a practical method for the synthesis of vinylcarba-zoles via iridium-catalyzed vinylation of carbazoles with vinyl acetate as the vinyl source. This simple and efficient reaction using an iridium catalyst provides a convenient method for producing monomers for the synthesis of poly(N-vinylcarbazole) s, which are used in electroluminescent devices.

DOI： 10.1055/s-0036-1588927

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

We report methylations of alcohols and anilines catalyzed by DMFstabilized Ir nanoclusters using methanol as the C1 source. The DMFstabilized Ir nanoclusters were prepared in one step and have diameters of 1-1.5 nm. They react in a borrowing-hydrogen reaction and are efficient methylation catalysts (TON up to 310000).

DOI： 10.1039/c6cc09279a

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

We report the catalysis of a Sonogashira-Hagihara cross-coupling reaction using a DMF-stabilized copper nanoparticle catalyst. The reaction proceeded with low catalyst loadings, and a turnover number of 4.0 x 10(3) was recorded for 0.01 mol% catalyst loading. DMF-stabilized copper nanoparticles thus showed high catalytic activity.

DOI： 10.1039/c6ra27910d

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

In this study, we report a thiolate-protected Au nanocluster, Au-25(phenylethanethiol)(18) [Au-25(PET)(18)], which serves as an efficient catalyst by a three-component coupling reaction (A(3) reaction) of aldehydes, amines, and alkynes to give the corresponding propargylamines in good to excellent yields.

DOI： 10.1246/cl.160813

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Language：English   Publisher：SPRINGER INTERNATIONAL PUBLISHING AG  

The development of practical, efficient, and atom-economical methods for the formation of carbon-carbon bonds remains a topic of considerable interest in current synthetic organic chemistry. In this review, we have summarized selected topics from the recent literature with particular emphasis on C-alkylation processes involving hydrogen transfer using alcohols as alkylation reagents. This review includes selected highlights concerning recent progress towards the modification of catalytic systems for the alpha-alkylation of ketones, nitriles, and esters. Furthermore, we have devoted a significant portion of this review to the methylation of ketones, alcohols, and indoles using methanol. Lastly, we have also documented recent advances in beta-alkylation methods involving the dimerization of alcohols (Guerbet reaction), as well as new developments in C-alkylation methods based on sp 3 C-H activation.

DOI： 10.1007/s41061-016-0012-8

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Language：English   Publisher：WILEY-V C H VERLAG GMBH  

Niobium complexes in organic reactions have received a lot of attention in recent years. Niobium is one of the early transition metals, which possess unique reactivity distinct from that of other transition metals. This review focuses mainly on stoichiometric reactions and catalytic reactions involving niobium complexes. In particular, recent results relating to Nb-V-mediated or Nb-III-catalyzed [2+2+2] cycloaddition of unsaturated compounds (alkyne, alkenes, nitriles, and isocyanates) are mainly presented in this review. In one example of a set of catalytic reactions involving a low-valent niobium species, the reaction between NbCl5 and tris(trimethylsilyl)silane generated a low-valent niobium(III) species, and this promoted [2+2+2] cycloaddition of terminal alkynes and olefins to provide cyclohexa-1,3-dienes. In addition, the use of low-valent niobium(III) species in stoichiometric reactions has also been reported. Many of these reactions are carried out by formation of Nb-alkyne complexes through reactions between low-valent niobium(III) and internal alkynes. Some examples of the use of Nb complexes as Lewis acids have also been reported. In these reactions, the valence of the Nb complexes is V.

DOI： 10.1002/ejoc.201500358

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

A Pd-catalyzed oxidative silylation of simple olefins with hexamethyldisilane to give allylsilanes has been achieved using molecular oxygen as the sole oxidant. The reaction provides a useful protocol to access synthetically useful allylsilanes from easily accessible simple olefins and hexamethyldisilane without using any oxidants other than O-2.

DOI： 10.1021/acs.joc.5b01216

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

NbCl5-mediated amidation of olefins with nitriles was successfully achieved. Various aliphatic, cyclic, and aromatic olefins, and various aliphatic and aromatic nitriles were used in this reaction to give secondary amides in high yields. (C) 2014 Elsevier B.V. All rights reserved.

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

We report the use of a DMF reduction method for straightforward synthesis of binary solid solution Cu-Pd nanoparticles (NPs) over the entire range of composition. The resulting NPs were uniform in size (less than 2.5 nm), tunable in composition, and exhibited photoluminescence properties that were nonlinear in composition. These binary solid solution NPs showed enhanced photoluminescence intensity and quantum yield compared to those of the single-metal NPs and their mixtures. The highest quantum yield of 3.10% for Cu-Pd alloy NPs synthesized using equimolar feeding ratio versus 2.75% for Cu and 0.71% for Pd NPs was obtained. These enhancements make the alloy NPs promising materials for optical applications.

DOI： 10.1039/c4tc02129k

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Language：English   Publisher：AMER CHEMICAL SOC  

This paper summarizes recent advances in a-alkylation reactions based on hydrogen borrowing methodologies using alcohol as an alkylating agent. This review provides a summary of recent progress toward the a-alkylation of carbonyl substrates, as well as relatively unactivated substrates bearing fewer acidic a-hydrogens, such as acetonitriles, acetamides, esters, methylpyrimidines, and methylquinolines. A summary of recent improvements in a-methylation strategies based on hydrogen borrowing methodologies has also been provided. Particular emphasis has been placed on highly practical and green chemistry approaches involving modified catalytic systems, including metal-supported heterogeneous catalysts and nanoparticle-based catalysts, as well as reactions conducted in the absence of a transition-metal catalyst. A review of recent achievements in methylation strategies using methanol as a methyl source, and their application to the a-methylation of ketones using transition-metal catalyzed hydrogen borrowing methodology, has also been documented.

DOI： 10.1021/cs501269d

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

This review consists mainly of stoichiometric reaction and catalytic reaction using niobium complexes. As an example of stoichiometric reaction, synthesis of 1H-indenes from the reaction of aliphatic ketones and aryl-substituted alkynes in the presence of stoichiometric amount of NbCl3(DME) has been documented. Alternatively, development of catalytic reaction of using low-valent Nb is intriguing. Our research group reported that low-valent Nb catalyzed intermolecular [2+2+ 2] cycloaddition reaction of alkynes with alkenes leading to tri- or tetra-substituted 1,3-cyclohexadienes in chemo- and regioselectivity. In addition, low-valent Nb catalyzed cycloaddition reaction of tert-butylacetylene with aryl-substituted nitriles to tri-substituted pyridines has been reported.

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Language：English   Publishing type：Part of collection (book)   Publisher：Elsevier Ltd.  

A variety of reaction examples and the method for the oxidation of C-H bonds adjacent to oxygen atom of ethers have been illustrated. Ethers are well known to be subject to autoxidation under the influence of molecular oxygen to generate peroxides or their decomposed products. Ethers are converted into aldehydes, carboxylic acids, ketones, and esters by the action of various oxidants including metallic oxidants such as chromium-based reagents, peroxide, ozone, and molecular oxygen. Electrochemical oxidation is adopted in the oxidative functionalization of C-H bonds neighboring to oxygen atom of ethers. The application of ether oxidation to the C-C bond formation in total synthesis and asymmetric synthesis has been documented. © 2014 Elsevier Ltd. All rights reserved.

DOI： 10.1016/B978-0-08-097742-3.00710-2

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

We developed a simple strategy for the synthesis of arylacetonitriles from benzyl chlorides and trimethylsilyl cyanide using a Ni( cod)(2)/PPh3 catalyst.

DOI： 10.1039/c4ra01153h

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

Iridium-catalyzed selective alpha-dimethylation and alpha-methylation of ketones or phenylacetonitriles, using methanol as the methylating agent, were achieved. In addition, three-component cross alpha-methyl-alkylation was successfully performed using methyl ketones with methanol and primary alcohols with long-chain alkyl groups. This method provides a very convenient direct route to alpha-methylated ketones, using methanol.

DOI： 10.1039/c3cc49626k

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

N,N-Dimethylformamide-stabilized palladium nanoclusters showed high catalytic activity for Migita-Kosugi-Stille cross-coupling reactions. The present cross-coupling reaction proceeded efficiently using very small Pd catalyst loadings under ligandless, and even an open air, conditions. The reactions proceeded smoothly in good yields and with high turnover numbers of up to 3.5 x 10(4). (C) 2013 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jorganchem.2013.08.004

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Language：Japanese   Publisher：The Adhesion Society of Japan  

DOI： 10.11618/adhesion.49.171

CiNii Books

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

DOI： 10.1002/cctc.201200649

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DOI： 10.1007/s11051-012-1379-2

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

Iridium-catalyzed alkylation of methylquinolines at the methyl substituent was achieved using alcohols as alkylating agents. The reaction proceeded through a transfer hydrogenation pathway from the alcohol to the Ir complex, affording an aldehyde and Ir-H species, followed by base assisted aldol condensation and hydrogenation. This method provides an atom-economical and convenient route to alkylquinolines from easily accessible methylquinolines.

DOI： 10.1021/jo3019347

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

Intermolecular cycloadditions of alkynes (terminal alkynes and internal alkynes) with aryl nitriles were successfully achieved, using an NbCl5 complex, to give substituted pyrimidine derivatives in high yields with excellent chemo- and regioselectivity.

DOI： 10.1021/om300669s

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Language：Japanese   Publishing type：Research paper (bulletin of university, research institution)  

J-GLOBAL

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

DOI： 10.1002/cctc.201100375

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

An iridium-catalyzed coupling reaction of alcohols with enones has been successfully developed providing access to 1,3-diketones with high selectivity in good yields. This reaction provides an atom-economical route to 1,3-diketones from readily available alcohols.

DOI： 10.1039/c2cc32787b

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

Surfactant-free, single-nano-sized copper nanoparticles (Cu NPs) (size: about 2 nm) were prepared by the DMF reduction method. The Cu NPs showed high catalytic activity (with a turnover number (TON) of up to 2.2 X 10(4)) in Ullmann-type cross-coupling of aryl halides with phenols under ligand-free conditions.

DOI： 10.1039/c2cc30975k

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

In this study, we investigated the catalytic properties of N,N-dimethylformamide (DMF)-stabilized gold nanoclusters (AuNCs) in the reduction of 4-nitrophenol (PNP) to 4-aminophenol by NaBH4, a well known model reaction to be catalyzed by metal surfaces. The DMF-stabilized AuNCs were prepared in DMF by a surfactant-free method. The DMF-stabilized AuNCs showed high catalytic activity even when used in small quantities (similar to 10(-7) g). The pseudo-first-order rate constant (k(app)) and activation energy were estimated to be 3 x 10(-3) s(-1) and 31 kJ mol(-1), respectively, with 1.0 mu M of the gold catalyst at 298 K. The catalytic activity of the DMF-stabilized AuNCs was strongly influenced by the layer of adsorbed DMF on the Au NCs. This layer of adsorbed DMF prohibited the reactants from penetrating to the surface of the AuNCs via the diffusion at the beginning of the reaction, resulting in an induction time (t(0)) before PNP reduction began. Restructuring of the DMF layer (essentially a form of activation) was the key to achieving high catalytic activity. In addition, atomically monodisperse Au-25(SG)(18)NCs (SG: glutathione) showed higher catalytic activity in the PNP reduction (k(app) = 8 x 10(-3) s(-1)) even with a low catalyst concentration (1.0 mu M), and there was no induction time (t(0)) in spite of the strongly binding ligand glutathione. This suggested that the catalytically active surface sites of the Au-25(SG)(18)NCs were not sterically hindered, possibly because of the unique core-shell-like structure of the NCs. Retaining these open sites on AuNCs may be the key to making the NCs effective catalysts.

DOI： 10.1039/c2nr30222e

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

Acetonitrile is successfully alkylated with primary and secondary alcohols in the presence of t-BuOK using [Ir(OH)(cod)](2) as a catalyst. This method provides a very clean and atom-economical convenient direct route to substituted nitriles, which are very important raw materials in organic and industrial chemistry.

DOI： 10.1246/cl.2011.1055

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：GEORG THIEME VERLAG KG  

This account gives an overview of iridium-catalyzed reactions developed by our group using mainly alcohols and diols as substrates. In the presented reactions, the iridium catalyst serves as a hydrogen acceptor from the alcohols giving iridium hydride, which is a key transient species. Herein, we report hydrogenation, alkylation, esterification, N-heterocyclization, and coupling reactions using alcohols and diols as reagents.

DOI： 10.1055/s-0030-1259094

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

DOI： 10.1002/anie.201104452

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A selective method for 2-aryl-2H- and 4-aryl-4H-3,5-diformylpyrans synthesis from 1,1,3,3-tetramethoxypropane and aromatic aldehydes was developed using an FeClcatalyst in MeOH-AcOH and an AlClcatalyst in DMA-AcOH. © Georg Thieme Verlag Stuttgart.

DOI： 10.1055/s-0030-1259681

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

Surfactant-free Pd nanoclusters (Pd NCs) (size: 1-1.5 nm) showed high catalytic activity in the Suzuki-Miyaura cross-coupling and Mizoroki-Heck reactions. The Pd NCs had a high turnover number, up to 6.0 x 10(8), which can be recycled at least five times without loss of catalytic activity.

DOI： 10.1039/c1cc11487e

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

Intermolecular [2+2+2] cycloaddition of tert-butylacetylene with alpha,omega-dienes was successfully achieved by NbCl3(DME) catalyst to afford 5-omega-alkenyl-1,4-disubstituted-1,3-cyclohexadienes in excellent yields with high chemo- and regioselectivity.

DOI： 10.1021/jo101229u

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Language：English   Publisher：MOLECULAR DIVERSITY PRESERVATION INTERNATIONAL-MDPI  

The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc)(2)/molybdovanadophosphoric acid (HPMoV) as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

DOI： 10.3390/molecules15031487

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

Acetates were successfully alkylated with primary alcohols and alpha,omega-diols in the presence of tert-BuOK Under the influence of [IrCl(cod)](2). For instance, the reaction of tert-butyl acetate with eta-butanol in the presence of tert-BuOK as a base and [IrCl(cod)](2) as a catalyst in tert-BuOH at 100 degrees C produced tert-butyl hexanoate in good yield. When the alpha,omega-diol 1,9-nonanediol was employed, di-tert-butyl tridecanoate was obtained. These reaction,; are the first report of the alkylation of acetates Using alcohols as alkylating agents. This method provides a very convenient direct route to carboxylates, which are very important raw materials in organic and industrial chemistry.

DOI： 10.1021/ja9106989

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

Synthesis of omega-hydroxy carboxylic acids and alpha,omega-dimethyl diketones was successfully achieved by using alpha,omega-diols as alkylating agents under the influence of an iridium catalyst. For example, the alkylation of butyl cyanoacetate with 1,13-tridecanediol in the presence of [IrCl(cod)](2) or [IrCl(coe)(2)](2) gave rise to butyl 2-cyano-15-hydroxypentadecanoate in good yield which is easily converted to cyclopentadecanolide (CPDL). In addition, the alkylation of acetone with 1,10-decanediol in the presence of [IrCl(cod)](2) and KOH resulted in an important muscone precursor, 2,15-hexadecanedione (HDDO), in good yield.

DOI： 10.1021/jo9027165

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

Intermolecular aerobic oxidative allylic amination of simple alkyl alkenes with simple amines such as diphenylamine was induced by a Pd(OCOCF3)(2)/NPMoV catalytic system, leading to the corresponding (E)-allylamines In good yield and selectivity through the formation of (eta(3)-allyl)palladium(II) trifluoroacetate species as a possible key intermediate.

DOI： 10.1021/ol100292g

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

A facile direct synthesis of cinnamonitriles from acrylonitriles and benzenes is successfully achieved by using Pd(OAc)(2)/HPMoV/O-2 catalyst system via the direct C-H bond activation of benzenes using molecular oxygen as a terminal oxidant.

DOI： 10.1039/c0ob00176g

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

A novel iridium-catalyzed intermolecular coupling reaction of primary alcohols or aldehydes with 2-alkynes was successfully achieved with high regioselectivity to give hydroacylation products such as alpha,beta-unsaturated ketones in good yields. The mechanistic investigation of the reaction strongly indicated that the coupling proceeds through the initial formation of homoallylic alcohols followed by dehydrogenation to beta,gamma-unsaturated ketones and then isomerisation, which leads to the hydroacylation products.

DOI： 10.1002/chem.200902646

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

A facile direct synthesis of (E)-alpha-cyanocinnamaldehydes from acrylonitrile and benzaldehydes is successfully achieved in a mixed solvent of EtOH/AcOH by Pd(OAc)(2)/HPMoV/FeCl3/O-2 catalyst system. The reaction was found to proceed via the cross-aldol condensation of diethyl acetal derived from acrylonitrile with aldehydes.

DOI： 10.1021/jo9021293

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

Ethanol was efficiently converted to ethyl and methyl acetates by [Cp*IrCl2](2) combined with 2-(methylamino)ethanol and a base like Cs2CO3 at room temperature in acetone in high yield, which provides the first Ir-catalyzed direct route to ethyl and methyl acetates from ethanol.

DOI： 10.1246/cl.2009.1106

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

A novel and efficient intermolecular aerobic oxidative amination of electron-deficient olefins with secondary aromatic amines has been successfully achieved by a Pd(II)/NPMoV/HQ-catalyzed reaction under dioxygen.

DOI： 10.1021/ol902052z

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

Synthesis and characterization of a series of mono-O-(diphenylphosphinobenzyl)calix[6]arenes are presented. The two types of calix[6]arene moieties were prepared: I (with tert-butyl groups at the upper rim) and 2 (without the tert-butyl groups). With regard to the position of a phosphorus atom, the diphenylphosphino group was introduced onto the ortho, meta, or para positions with the benzyl ether moiety. These phosphines as well as their oxides were fully characterized by elemental analysis, NMR measurements, and HR-ESI-MS. The NMR study indicated that I had a cone conformation whereas 2 was very flexible in solution. These phosphines were found to be effective ligands in Rh-catalyzed hydroformylation.

DOI： 10.1246/bcsj.82.1187

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We report iridium-catalyzed coupling of 2-alkynes such as 1-aryl-1-propynes with primary alcohols leading to secondary homoallylic alcohols as products. This reaction involves an iridium-catalyzed novel catalytic transformation of 2-alkynes and primary alcohols through the formation of hydrido(pi-allyl)iridium as a possible key intermediate.

DOI： 10.1021/ol901366q

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

Acetals like 3,3-diethoxypropionate bearing electron-withdrawing groups were found to undergo cyclodimerization and cyclotrimerization in the presence of Lewis acids to give coumalates and 1,3,5-trisubstituted benzenes. The selectivity of these products depended on the Lewis acids employed. For instance, ethyl coumalate was obtained from ethyl 3,3-diethoxypropionate in high selectivity under the influence of d-block Lewis acids like FeCl(3), whereas triethyl 1,3,5-benzenetricarboxylate was obtained in preference to ethyl coumalate under the influence of lanthanoid Lewis acids like GdCl(3). Various coumalates were synthesized by the FeCl(3)-catalyzed cross-cyclodimerization of acetals with active methylene compounds. From 4,4-dimethoxy-2-butanone, however, 1,3,5-triacetylbenzene, which is difficult to prepare regioselectively by conventional methods, was formed in quantitative yield under the influence of AlCl(3). This reaction would provide a very convenient route to 1,3,5-triacetylbenzene. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

DOI： 10.1002/ejoc.200900432

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Ethanol was efficiently converted into n-butanol in the presence of a catalytic amount of [Ir(acac)(cod)], 1,7-octadiene, and EtONa. This method provides an efficient alternative approach to n-butanol which is conventionally manufactured by oxo process of propylene with H-2 and CO followed by hydrogenation of butyraldehyde.

DOI： 10.1246/cl.2009.838

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One-pot Baeyer-Villiger oxidation of cycloalkanones was successfully achieved by allowing them to react with hydrogen peroxide generated in situ from benzhydrol and molecular oxygen assisted by N-hydroxyphthalimide (NHPI) and 2,2'-azobisisobutyronitrile (AIBN). This method provides an alternative synthetic route to lactones from cycloalkanones using sec-alcohols and molecular oxygen assisted by NHPI.

DOI： 10.1246/bcsj.82.891

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Acetophenones substituted by alkyl, alkoxy, acetoxy, and halogen groups were selectively oxidized with molecular oxygen to the corresponding benzoic acids by using the N,N',N ''-trihydroxyisocyanuric acid (THICA)/cobalt(II) acetate [Co(OAC)(2)] anese(II) acetate and THICA/Co(OAc)(2)/manganese(II) [Mn(OAc)(2)]. For example, 4-methylacetophenone was selectively oxidized with molecular oxygen to 4-acetylbenzoic acid (85%) by THICA/Co(OAc)(2) and to 4-methylbenzoic acid (93%) by Mn(OAc),, while terephthalic acid was obtained in 93% with the THICA/Co(OAc)(2)/Mn(OAc)(2) catalytic system. It is interesting that the acetyl group Oil the aromatic ring is efficiently converted by a very small amount of Mn(OAc)(2) to the corresponding carboxylic acid. and that the present method provides a versatile route to acetylbenzoic acids which are difficult to prepare by conventional methods.

DOI： 10.1002/adsc.200900099

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The Beckmann rearrangement of ketoximes to lactams was successfully achieved by a very small amount of cyanuric chloride and phosphazene by carrying out the reaction in a mixed solvent of trifluoroacetic acid and toluene under mild conditions. For instance, the Beckmann rearrangement of cyclohexanone oxime was completely performed under the influence of 0.5 mol % of cyanuric chloride (CNC) or phosphazene (1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride: TAPC) in a 3:2 mixed solvent of trifluoroacetic acid and toluene at 70 degrees C for 4 h to give E-caprolactam., which is an important monomer of 6-Nylon, in almost quantitative yield. The same strategy could be applied to lauro-lactam synthesis from cyclododecanone oxime.

DOI： 10.1021/op800258s

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A new strategy to 6-hydroxy-2-naphthoic acid (HNPA) and 4-hydroxybenzoic acid from 2,6-diisopropylnaphthalene and p-cymene, respectively, was developed using the NHPI-catalyzed aerobic oxidation as a principal reaction. 2,6-Diisopropylnaphthalene was oxidized by the oxidation with O(2) (1 atm) by NHPI (10 mol %) combined with Co(OAc)(2) (0.5 mol %) to give 6-acetyl-2 -isopropylnaphthalene, which then was converted to 6-isopropyl-2-naphthoic acid Under O(2) (1 atm) in the presence of Co(OAc)(2) (0.5 mol %) and Mn(OAc)(2) (0.5 mol %), Esterification of the resulting acid followed by the aerobic oxidation produced methyl 6-hydroxy-2-naphthoate whose hydrolysis led to the desired HNPA. An alternative route involves the oxidation of 6-acetyl-2-isopropylnaphthalene to 6-acetyl-2-naphthol on which subsequent oxidation and deacetylation gave HNPA. This method was Successfully extended to the synthesis of 4-hydroxybenzoic acid from p-cymene. (C) 2009 Elsevier Ltd, All rights reserved.

DOI： 10.1016/.j.tet.2009.03.013

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Benzoquinoline derivatives were successfully synthesized by iridium-catalyzed N-heterocyclization of naphthylamines with diols. For instance, the reaction of 1-naphthylamine with 1,3-propanediol catalyzed by IrCl(3) combined with BINAP as a ligand produced 7,8-benzoquinoline in quantitative yield. The N-heterocyclization reaction was found to be markedly influenced by the ligands employed. Benzoindoles were also synthesized by the same strategy from napthylamines with 1,2-diols. A reaction mechanism for the N-heterocyclization of naphthylamines with 1,3-diols by IrCl(3) was proposed.

DOI： 10.1021/jo801966u

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NbCl3(DME)-catalyzed [2+2+2] intermolecular cycloaddition of alkynes and alkenes was successfully achieved to give 1,4,5-trisubstituted-1,3-cyclohexadiene derivatives in good yields.

DOI： 10.1039/b820352k

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

New strategies for lactams synthesis from cycloalkanes without formation Of sulfates have been proposed. The synthesis of lactams from cycloalkanes through a one-pot reaction was successfully performed using N-hydroxyphthalimide (NHPI) as a key catalyst. The strategy involves nitrososation of cycloalkanes with tert-butyl nitrite under the influence of NHPI followed by isomerization to oximes and then the Beckmann rearrangement to lactams. For example, E-caprolactam and laurolactam were prepared from cyclohexane and cyclododecane in 74% and 78% yields, respectively, in one-pot. An alternative approach for sulfate-free lactam synthesis includes the nitration of cyclohexane with NO, to nitrocyclohexane in the presence of NHPI under mild conditions followed by the hydrogenation to cyclohexanone oxime. The Beckmann rearrangement to epsilon-caprolactam was found to be achieved in quantitative yields by a very small amount of cyanuric chloride in a mixed solvent of trifluoroacetic acid and toluene.

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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.

DOI： 10.1016/j.tetasy.2008.06.034

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The N-hydroxyphthalimide derivatives, F(15)- and F(17)-NHPI, bearing a long fluorinated alkyl chain, were prepared and their catalytic performances were compared with that of the parent compound, N-hydroxyphthalimide (NHPI). The oxidation of cyclohexane under 10 atm of air in the presence of fluorinated F(15)- or F(17)-NHPI, cobalt diacetate [Co(OAc)(2)], and manganese diacetate [Mn(OAC)(2)] without any solvent at 100 degrees C afforded a mixture of cyclohexanol and cyclohexanone (K/A oil) as major products along with a small amount of adipic acid. It was found that F(15)- and F(17)-NHPI exhibit higher catalytic activity than NHPI for the oxidation of cyclohexane without a solvent. However, for the oxidation in acetic acid all of these catalysts afforded adipic acid as a major product in good yield and the catalytic activity of NHPI in acetic acid was almost the same as those of F(15)- and F(17)-NHPI. The oxidation by F(15)- and F(17)-NHPI catalysts in trifluorotoluene afforded K/A oil in high selectivity with little formation of adipic acid, while NHPI was a poor catalyst under these conditions, forming K/A oil as well as adipic acid in very low yields. The oxidation in trifluorotoluene by F(15)- and F(17)-NHPI catalysts was considerably accelerated by the addition of a small amount of zirconium(IV) acetylacetonate [Zr(acac)(4)] to the present catalytic system to afford selectively K/A oil, but no such effect was observed in the NHPI-catalyzed oxidation in trifluorotoluene.

DOI： 10.1002/adsc.200800057

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Direct conversion of benzene to phenol was achieved by allowing it to react with a mixed gas of air and CO in the presence of HPMoV and a very small amount of Pd-5%/C in aqueous acetic acid at 150 degrees C for 2h. The TON of HPMoV for the formation of phenol goes up to over 1300. The active species of the present reaction is thought to be V4+ generated from HPMoV catalyst by the reduction with CO. The role of the I'd species seems to promote the generation of V4+ from HPMoV. This method is expected to provide a direct route to phenol from benzene. (C) 2008 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.molcata.2008.04.002

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omega-Hydroxy ketones and diketones, which are important starting materials for the synthesis of cycloalkanones and heterocyclic compounds, were prepared by the one-step reaction of methyl ketones with alpha,omega-diols under the influence of an iridium complex and a base. The selectivity of omega-hydroxy ketones and diketones could be controlled by varying the starting ratio of methyl ketones to alpha,omega-diols. For example, reaction using acetophenone (5 equiv) with respect to 1,6-hexanediol (1 equiv) in the presence of [IrCl(cod)](2), PPh3, and KOH without solvent gave 1,10-diphenyl-1,10-decanedione in almost quantitative yield, while reaction using acetophenone (1 equiv) to 1,6-hexanediol (4 equiv) led to 8-hydroxy-1-phenyl-1-octanone in 92% yield. This methodology was successfully extended to the reaction of arylacetonitriles with alpha,omega-diols leading to diaryldinitriles.

DOI： 10.1246/bcsj.81.689

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Triphosphazene, 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride (TAPC), was found to be an efficient catalyst for the Beckmann rearrangement of cyclohexanone oxime and cyclododecanone oxime to E-caprolactam and laurolactam, which are raw materials of nylon-6 and nylon-12, respectively.

DOI： 10.1021/jo702277g

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Carboxylation of benzenes with CO was successfully achieved by a combined catalytic system of Pd(OAc)(2) with H5PMo10V2O40-nH(2)O (HPMo10V2) under the influence of O-2 to form the corresponding benzoic acids in relatively high selectivity and moderate yields. The regioselectivity in the carboxylation of alkylbenzenes with CO was dominated by the steric factor rather than the electronic effect of substituents. However, the carboxylation of benzoic acid proceeded with high ortho-selectivity to give phthalic acid in preference to terephthalic acid, which shows coordination of Pd species to the carboxyl group of benzoic acid. (C) 2007 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.molcata.2007.11.022

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Various substituted phenols were selectively synthesized by a one-pot reaction through the NHPI-catalyzed aerobic oxidation of 1,1-diarylethanes followed by treatment with dilute sulfuric acid.

DOI： 10.1039/b804055a

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Oxidative arylation of ethylene with benzene was examined by using a Pd(OAc)(2)/heteropoly acid/O(2) system under mild conditions. The reaction of benzene with ethylene in the presence of catalytic amounts of Pd(OAc)(2) combined with H(4)PMo(11)VO(40) center dot 15H(2)O (or H(3)PMo(12)O(40) center dot 30H(2)O), AcONa, and dibenzoylmethane under air at 90 - 120 degrees C produced oxidative coupling products, styrene and stilbene, in fair yields (up to 167 total turnovers). From the examination of the catalyst performance of Pd(OAc)(2) combined with various heteropoly acids, it was found that the employment of heteropoly acids including molybdenum ion in their structure is very important to obtain high turnover numbers of Pd.

DOI： 10.1039/b716425d

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A new synthetic method of substituted furoates from acrylates and aldehydes was developed by Pd-(OAc)(2) combined with molybdovanadophosphoric acid and Lewis acid under atmospheric dioxygen. The reaction was found to proceed through the palladium-catalyzed acetalization of acrylates with methanol followed by the reaction of the resulting acetals with aldehydes.

DOI： 10.1021/jo701635f

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A new type of carbonylation of styrenes was achieved under a 1: 1 mixture of CO (0.5 atm) and O-2 (0.5 atm) in the presence of Pd(OAc)(2) combined with H5PMo10V2O40 center dot nH(2)O to give 4-methyl-2-phenylnaphthalen-1(4H)-one in 78 % yield. Various substituted styrenes were also carbonylated to the corresponding substituted arylnaphthalen-1(4H)-ones in moderate yields. The reaction was found to proceed in two stages involving the head-to-tail dimerization of styrenes, followed by carbonylation of the resulting dimers. Styrenes were efficiently dimerized under air (1 atm) in the absence of CO even at room temperature to produce head-to-tail dimers in good yields.

DOI： 10.1246/bcsj.80.1194

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A new type of trisannelation reaction of acrylates through acetal formation was developed by Pd(OAc)(2) combined with molybdovanadophosphoric acid (HPMo8V4) and Lewis acid under atmospheric dioxygen. Thus, the reaction of isobutyl acrylate in the presence of Pd(OAc)(2), HPMo8V4, and CeCl3 under O-2 (1 atm) in MeOH/AcOH afforded isobutyl 1,3,5-benzenetricarboxylate in fair yield. The reaction was found to proceed through the palladium-catalyzed acetalization of acrylate with methanol followed by the trisannelation reaction of the resulting acetal promoted by CeCl3.

DOI： 10.1021/jo070323e

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Metal complexes-catalyzed hydrolysis and alcoholysis of organic substrates such as alkenyl esters, alkenyl ethers, and azlactones (oxazol-5(4H)-ones) are described. These reactions were applied for kinetic resolution of chiral compounds and high selectivities were achieved with vinyl ethers of 2-substituted cyclohexanols, 1,1'-bi-2-naphthols, 1,1'-bi-2-phenols, and 4,4-disubstituted aziactones. Oxidative carbon-carbon bond cleavage reactions, which were found in the course of the study of asymmetric hydrolysis were also described. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jorganchem.2006.06.045

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Bowl-shaped phosphine ligands were found to be highly effective in Suzuki-Miyaura coupling of unactivated aryl chlorides, in which the depth of the bowl affected the catalytic activity considerably.

DOI： 10.1021/ol0626138

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Novel rhodium(I) complexes with N-heterocyclic carbenes bearing a 2,3,4,5-tetraphenylphenyl and its higher dendritic frameworks were synthesized and the complexes were used as catalysts in rhodium-catalyzed hydrosilylation of alpha, beta-unsaturated ketones to show high 1,4-adduct selectivity.

DOI： 10.1039/b612385f

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Rh(III) complexes with a bidentate N-heterocyclic carbene ligand bearing flexible dendritic frameworks have been synthesized and fully characterized by X-ray crystallographic analysis, NMR measurements and theoretical calculations.

DOI： 10.1039/b701104k

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Base-free catalytic alpha-alkylation of active methylene compounds with primary alcohols was successfully achieved using an [IrCl(cod)] complex in the presence of PPh3 to afford the corresponding saturated alpha-alkylated products in good yields.

DOI： 10.1039/b702293j

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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.

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Primary alcohols undergo efficiently oxidative dimerization by iridium complexes under air without any solvent to form esters in fair to good yields. For instance, the reaction of 1-dodecanol in the presence of [IrCI(coe)(2)](2) (3 mol %) at 95 degrees C for 15 h produced dodecyl dodecanoate in 91% isolated yield. This is the first successful Ir-catalyzed oxidative dimerization of primary alcohols to esters using air as an oxidant. Various primary alcohols are converted to the corresponding esters in fair to good yields. (c) 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2006.10.144

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[IrCl(cod)](2) and [Cp*IrCl(2)](2) complexes catalyzed efficiently the Guerbet reaction of primary alcohols to beta-alkylated dimer alcohols in good yields. For instance, the reaction of 1-butanol in the presence of [ Cp*IrCl(2)](2) (1 mol %), t-BuOK (40 mol %), and 1,7-octadiene (10 mol %) produced 2-ethyl1- hexanol in 93% yield. Various primary alcohols undergo the Guerbet reaction under the influence of Ir complexes to give the corresponding dimer alcohols in good yields. This method provides an alternative direct route to beta-alkylated primary alcohols which are prepared by aldol condensation of aldehydes followed by hydrogenation.

DOI： 10.1021/jo061400t

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Three new triarylphosphines were prepared that have a 2,3,4,5-tetraphenylphenyl (TPPh) moiety on one of the phenyl rings (at the ortho, meta, or para position) of triphenylphosphine. Among them, the ortho derivative is particularly effective to utilize unactivated aryl chlorides in three different palladium-catalyzed reactions, i.e., Suzuki-Miyaura coupling, Mizoroki-Heck reaction, and silylation with Me3SiSiMe3. On the other hand, the corresponding meta and para derivatives are not effective as ligands at all in these catalytic reactions. X-ray crystal structures of Pd(0) complexes having the effective phosphines (ortho derivatives) as ligands show that eta(2)-coordination on the TPPh moiety is general and operative to realize a highly active catalyst system.

DOI： 10.1021/om060615q

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Nickel- catalyzed cross-coupling reactions of Nb(III)-alkyne complexes with aryl iodides are reported, in which addition of lithium alkoxide is indispensable and diarylated coupling products are afforded as products.

DOI： 10.1021/om060065w

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Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with la afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the k(ret) values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.

DOI： 10.1021/ja058112j

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Novel phosphanylcalix[6]arenes having mono-O-diphenyl-phosphanylmethyl (3) and mono-O-(4-diphenylphosphanylphenyl)methyl substituents (5) have been synthesized. The structures of these monophosphanylcahx[6]arenes were determined by NMR spectroscopy, mass spectrometry, and Xray crystal structure analysis. The X-ray structure reveals that 3 adopts a flattened 1,2,3-alternate conformation in the crystalline state, while the NMR spectra show that 3 and 5 have a cone conformation in solution. Structure optimization and energy calculations for 3 and 5 at the B3LYP/LANL2DZCONFLEX5/MMFF94s level of theory show that the cone conformation is slightly more stable than the 1,2,3-alternate conformation by 0.36 kcal mol(-1) for 3 and 0.96 kcal mol(-1) for 5. Complexation of 3 with [PtCl2(COD)] and [Rh(COD)(2)]BF4 gives cis-coordinated [PtCl2(3)(2)] and [Rh(COD)(3)(2)]BF4, respectively. The X-ray analysis Of [PtCl2(3)(2)] shows that 3 adopts a cone conformation upon complexation. Combination of 3 and 5 with [Rh(COD)(2)]BF4 provides an active catalyst for the hydroformylation of a variety of terminal alkenes. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

DOI： 10.1002/ejic.200500673

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER/PLENUM PUBLISHERS  

Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition, several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic behavior with size-selective molecular recognition.

DOI： 10.1007/s10563-005-9160-5

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A novel C=C bond cleavage reaction of aromatic enol ethers (1) to give ketones (2) using molecular oxygen as oxidant is described. Among the examined catalysts (Cu(II), Pd(II), Ru(II), and H+), CuCl2 exhibited the highest activity. The reaction proceeded smoothly with several kinds of substrates. (c) 2005 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jorganchem.2005.05.018

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Oligomerization of Pd(OAC)(2)(L)(2) (L = pyridine derivatives), a catalyst for the air oxidation of alcohols, is studied with MALDI TOF mass, using dithranol as the matrix. The degree of the Pd oligomerization is influenced by the pyridine ligands, and this ligand effect is similar to one observed for Pd black formation in the catalysis.

DOI： 10.1021/ol051845o

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DOI： 10.1021/ja051750h

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Bowl-shaped phosphine (BSP) ligands markedly accelerated the rhodium-catalyzed hydrosilylation of ketones and ketimines as compared with the effect of conventional phosphine ligands such as PPh3 and P(t-Bu)(3). P-31 NMR study of a mixture of [RhCl(C2H4)(2)](2) and phosphines at various P/Rh ratios revealed that coordination of BSP to the rhodium metal was successfully regulated, and the resultant rhodium complex bearing only one phosphine ligand (a mono(phosphine) rhodium species) was responsible for the acceleration. Structural comparison between BSP and the conventional phosphines was carried out using HF/6-31G(d)-CONFLEX/MM3-optimized structures. The mono(phosphine) rhodium complex having 1,5-cyclooctadiene as a ligand was isolated, and its X-ray molecular structure was determined.

DOI： 10.1021/om0503491

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A novel capsule-shaped Ir(I) and Rh(I) cationic complexes with a triphosphinocalix[6]arene as a ligand were synthesized. These complexes showed dynamic behavior with size-selective molecular encapsulation, which was confirmed by variable-temperature P-31{H-1} NMR measurement in the presence of various molecules.

DOI： 10.1021/om049227j

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A variety of 1,1,2-trisubstituted-1H-indenes are synthesized by the reaction of aliphatic ketones, aryl-substituted alkynes and NbCl3(DME) in 1,2-dichloroethane under reflux conditions.

DOI： 10.1039/b412519c

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

Novel dendrimer N-heterocyclic carbene complexes with rhodium(I) located at the core were synthesized, and a positive dendrimer effect was found in the hydrosilylation of ketones catalyzed by them.

DOI： 10.1039/b506927k

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Novel upper-rim modified tetraphosphinocalix[4]arenes (5a-b) adopting 1,3-alternate conformation have been synthesized. Reaction of 5,11,17,23-tetrachloromethyl-25,26,27,28-tetrahydroxycalix[4]arene (1) with Ph2POEt gave 5,11,17,23-tetrakis(diphenylphosphinoylmethyl)-25,26,27,28-tetrahydroxycalix[4]arene (2). Tetra-O-substitution of 2 with n-propyl iodide or benzyl bromide in the presence of K2CO3 carried out to afford 5,11,17,23-tetrakis(diphenylphosphinoylmethyl)-25,26.27,28-tetrapropoxy-(3a) or -benzyloxycalix[4]arene (3b), whereas di-O-substituted calix[4]arene, 5,11,17,23-tetrakis(diphenylphosphinoylmethyl)-25,27-dipropoxy-26,28-dihydroxycalix[4]arene (4), was obtained exclusively when Na2CO3 was used as base. Reduction of 3a-b with PhSiHCl2 afforded 5,11,17,23-tetrakis(diphosphinomethyl)-25,26,27,28-tetrapropoxy-(5a) and -tetrabenzyloxycalix[4]arene (5b). H-1 and C-13 NMR analysis reveals that the phosphines (5a-b) and the tetra-O-substituted phosphine oxides (3a-b) adopt 1,3-alternate conformation, while the parent tetrahydroxy-(2) and the di-O-propylated phosphine oxide (4) adopt cone-conformation. The X-ray structure indicates that the calix[4]arene moieties in 4 a pinched-cone conformation in solid state. Complexation of the phosphine ligand (5a) with [RuCl2(p-cymene)](2) affords the tetranuclear complexes, [{RuCl2(p-cymene)}(2)(.)5a] (6), as 1,3-alternate conformer. (C) 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ica.2004.03.037

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

DOI： 10.1021/ja0319361

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

Various kinds of transition metals catalyzed the hydrolysis of alkenyl esters and ethers under buffer-free, high concentration conditions compared to usual biocatalysts. Hydrolytic kinetic resolution of cis-2-tert-butylcyclohexyl vinyl ether was achieved by chiral (salen)Co complexes with good selectivity (k(rel) = 10.0).

DOI： 10.1021/ol036228j

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

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

The first cross-coupling reaction of thermally stable titanium( II)-alkyne complexes with aryl iodides in the presence of a catalytic amount of Ni(cod)(2) is presented.

DOI： 10.1039/b310565b

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

Recent progress in supramolecular transition metal catalysis is descried. Various supramolecular catalyst systems containing cyclodextrins, dendrimers, calixarenes, and other moieties published in 1999-2002 are reviewed.

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Language：English   Publisher：ELSEVIER SCIENCE SA  

In the presence of a catalytic amount (5 mol%) of a platinum complex, tributyltin cyanide (1) reacts with dimethyl-(2a) or diethyl acetylenedicarboxylate (2b) to afford cyanostannylation adducts (3a, b) in excellent yields. The reaction proceeds highly selectively affording only a (Z)-isomer. The compounds 3a, b are novel products which possess synthetically useful cyano, alkenylstannyl and alkoxycarbonyl. functionalities in the same molecule. Two alkoxycarbonyl functionalities may be indispensable on each alkyne carbon to accomplish the cyanostannylation reaction. Reaction with terminal alkynes gave the stannylated product (6). (C) 2002 Elsevier Science B.V. All rights reserved.

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

Palladium-catalyzed acylation of allylic trifluoroacetates (2) using acylstannanes (1) is reported. The reaction serves as a complementary method to the previously reported acylation with acylsilane (4). In particular, the reaction is profitable in the acylation of unsubstituted allyl trifluoroacetate (2a) and benzoylation of allylic trifluoroacetates to afford synthetically useful beta,gamma-unsaturated ketones (3) in good yields without undesirable isomerizations.

DOI： 10.1021/jo0202482

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

The synthesis and complexation behavior of a novel bis-phosphine ligand based on a calix[4]arene scaffold, 5,17-bis(diphenylphosphino)-25,26,27,28-tetrabenzyloxycalix[4]arene (3), are reported. Reaction of 3 with PdCl2(cod) under dilute conditions results in formation of the trans-coordinated dinuclear complex [PdCl2.3](2) (4). The X-ray structure of 4 reveals that the two phosphinocalix[4]arene molecules are linked by the two PdCl2 fragments. On the other hand, reaction of 3 with PtCl2(cod) affords the cis-chelating mononuclear complex PtCl2.3 (5). The X-ray structure, low-temperature NMR measurements, and geometry optimization of 5 reveal that the structure in solution at -80 degreesC and in solid-state has a C-1 symmetry where the P-Pt-P plane is inclined and the calix[4]arene moiety is twisted. It was also found that 3 reacts with [Pd(eta(3)-C3H5)(cod)]BF4 to yield the corresponding cationic complex [Pd(eta(3)-C3H5).3]BF4 (6) quantitatively. Low-temperature NMR measurements suggest that 6 exists as a mixture of two stereoisomers (6a and 6b) possessing a C-1 symmetry. Although both 5 and 6 exhibit C-1 structure at -80 degreesC, their NMR spectra measured at 20 degreesC indicate a C-2v symmetry for 5 and a C-s symmetry for 6. These fluxional behaviors of 5 and 6 in solution are caused by two separable motions: rollover motion of the coordination plane (R motion) and twist motion of the calix[4]arene scaffold (T motion).

DOI： 10.1021/om010882q

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Language：English   Publisher：AMER CHEMICAL SOC  

Preparation of novel mono- and bidentate phosphine ligands having dendrimer moiety is reported. Monodentate (1a-c) and bidentate ligands (5a,b) were synthesized from bis(4-hydroxyphenyl)phenylphosphine oxide (3) and 1,2-bis(dichlorophosphino)ethane, respectively, in high yields. The defect-free monodisperse nature of these compounds was confirmed by P-31 NMR and elemental analysis as well as by ESI mass spectra. Complexation of these ligands with PtCl2(COD) followed by NaBH4 reduction in a THF/H2O mixture gave Pt(0) complexes 10a,b (having la,b as the ligands) and 13a,b (5a,b as the ligands). Monodentate ligands gave PtL3 complexes (10a,b) and bidentate ligands gave Pt(L-L)(2) complexes (13a,b), respectively. Preliminary studies on oxidative addition of RI (R = CH3 or C6H5) to 10a,b showed that the metal center is easily accessible. Further, molecular modeling of 13b showed nanoscale flattened globular structure of the complex with an approximate diameter of 4.4 nm.

DOI： 10.1021/om010687b

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

Acylation of allylic esters (2) with acylsilanes (1) in the presence of a catalytic amount (5 mol %) of a palladium complex is reported. The reaction proceeds selectively to afford beta,gamma -unsaturated ketones (3) in high yields. [Pd(eta (3)-C6H5CH=CHCH2) (CF3COO)](2) (4a) showed the best catalytic activity. After the reaction, formation of CF3COOSiMe3 (5a) was confirmed by Si-29 NMR measurement of the resulting reaction mixture, indicating the trimethylsilyl moiety effectively traps the CF3COO leaving group from 2. The leaving group of the allylic esters affects the reaction considerably: allylic trifluoroacetate gave the best result, while the corresponding acetates and trichloroacetates did not afford any acylation products at all. Stoichiometric reaction of 4a with 1 gave acylation product 3 with a formation of 5a and Pd(0), whereas no acylation reaction took place with the corresponding acetate complex [Pd(eta (3) -C6H5CH=CHCH2)(CH3COO)](2) (4b). A DFT calculation suggests that interaction of high-lying HOMO of 1 and low-lying LUMO of eta (3)-allylpalladium trifluoroacetate intermediate 4 would be indispensable in the catalytic cycle.

DOI： 10.1021/ja010674p

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

X-ray crystallographic analysis and CPMAS solid-state NMR measurements of tetrakis(diphenylphosphino)calix[4]arene tetramethyl ether (1) elucidated that in the solid-state 1 adopts a flattened partial cone conformation having C, symmetry. In solution, on the other hand, the H-1, C-13, and P-31 NMR spectra measured at - 20 degreesC indicated that 1 has a partial cone conformation with a mirror plane. Two-dimensional P-31 EXSY and variable-temperature P-31 NMR spectra reveal a fluxional behavior of 1 in solution on the NMR time scale due to annulus rotation from the methoxy side. Concerning the energetics for the four conformers of 1, an ab initio molecular orbital calculation showed that the partial cone conformation is the most stable form, while the cone and the 1,3-alternate conformers are only slightly less stable.

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Language：English   Publisher：ELSEVIER SCIENCE SA  

Hexamethyldistannane reacts with Pt{P(MeC6H4)(3)}(4) at -30 degrees C to afford the oxidative addition product: cis-[Pt(SnMe3)(2){P(MeC6H4)(3)}(2)]. The structure is distinctly distorted from planarity: the dihedral angle between the P-Pt-P and the Sn-Pt-Sn planes is 34.6 degrees. The solution P-31-NMR spectra indicate that the complex shows reversible fluxional behavior. The fluxional process is attributed to the intramolecular twist-rotational motion via pseudo tetrahedral transition state. A similar fluxional process is observed with bis(silyl)bis(phosphine)platinum and bis(stannyl)bis(phosphine)palladium complexes. (C) 2000 Elsevier Science S.A. All rights reserved.

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

[GRAPHICS]
An equimolar mixture of propargylic carbonate (1) and trimethylsilyl cyanide (2) in THF under reflux affords cyanoallene (3) in the presence of a catalytic amount (5 mol %) of Pd(PPh3)(4). In the reaction, the trimethylsilyl moiety of 2 effectively traps the leaving group of 1. The use of 2 in excess (6 equiv) provides dicyanated products (7 or 8) in high yields.

DOI： 10.1021/ol006160x

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Complexes generated by treating chloro(aryloxy)bis(cyclopentadienyl)zirconium [3; aryloxy = 2,6-di-tert-butyl-4-methylphenoxy (3a), 2,6-diisopropylphenoxy (3b), phenoxy (3c), 2,3,4,5,6-pentafluorophenoxy (3d), and 2,6-dimethoxyphenoxy (3e)] with one equivalent of n-BuLi catalyze dehydrocoupling polymerization of arylsilanes 1 [aryl=phenyl (la), p-methoxyphenyl (Ib), p-dimethylaminophenyl (Ic), p-methylthiophenyl (Id)] at room temperature to afford corresponding polysilanes. Their catalytic performance was compared with the conventional system generated from dichlorobis(cyclopentadienyl)zirconium (4) and two equivalents of n-BuLi. The reaction of la using 3a/n-BuLi, 3b/n-BuLi or 3c/n-BuLi gave high-molecular-weight polysilanes (M(w) = 13.3 x 10(3) and M(n) = 5.8 x 10(3) with 3a; M(w) = 10.4 x 10(3) and M(n) = 4.2 x 10(3) with 3b; M(w) = 8.8 x 10(3) and M(n) = 5.3 x 10(3) with 3c). Formation of the polysilane was fast in comparison with 4, in particular when the catalyst was ligated by a sterically demanding (3a) or electron-withdrawing (34) aryloxy group. The time course of the gel permeation chromatography profiles suggested that complex 3a showed faster chain growth than 34, 3e and 4. The extent of the formation of undesired cyclics was relatively small(< 10%) in the sterically demanding 3a/n-BuLi- or 3b/n-BuLi-catalyzed reaction. (C) 2000 Elsevier Science S.A. All rights reserved.

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

Treatment of bis(phenylethynyl)silane (PhC=C)(2)SiR2 (R = Me (2a), Et (2b) or Ph (2c)) with Cp2ZrEt2 (1) (Cp = cyclopentadienyl) and H2O/CuCl in this order afforded (1E,3E)-1,4-diphenyl-1,3-butadiene (3) in 56-88% yields after hydrolysis. On the other hand, hydrolysis of the reaction mixture of 2a-h with Cp2ZrEt2 gave silacyclobutene derivatives 4a-h in 61-87% yields. Zirconium-containing intermediate 7 was obtained as crystals suitable for X-ray analysis when t-BuC5H4 was used as the ligands of a zirconocene derivative. Structure of 7 showed that the intermediate contained the zirconacyclobutene-silacyclobutene fused ring system. Reaction of silacyclobutene 4a with CuCl selectively opened the silacyclobutene ring. The further treatment of the reaction mixture with PhI in the presence of a catalytic amount of Pd(PPh3)(4) gave 1,3,4-triphenyl-1-silyl-1,3-butadiene compound 16. Zirconacyclopentadienes with an alkynylsilyl group at the alpha-position afforded zirconacyclohexadiene derivatives 19 in 82-98% yields. When t-BuC5H4 was used as the ligands instead of two Cp, the structure was determined by X-ray analysis. The structure clearly showed that 19 had the zirconacyclohexadiene-silacyclobutene fused ring system.

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

The synthesis and activity as precatalysts for stereoregular a-olefin polymerization of the chiral C-1-symmetric zirconocene complexes (R)- and (S)-Me2Si(eta(5)C(13)H(16))(eta(5)-C5H3R*)ZrR2, where C13H16 = octahydrofluorenyl, R = NMe2, Cl, or Me, and R* = (1R,2S,5R)-trans-5-methyl-cis-2-(2-propyl)cyclohexyl ((-)-menthyl), are described.

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

In this paper we report the Cp'(2)Ln/Me2SiCp''(2)Ln-catalyzed (Cp' = eta(5)-Me5C5; Cp'' = eta(5)-Me4C5) hydrogenation of acyclic imines to yield the corresponding amines. At 190 psi of H-2, the observed turnover frequencies (h(-1)) (100:1 substrate:catalyst ratio, Cp'(2)Ln, temperature (degrees C)) are (1) (N-benzylidene(methyl)amine, Ln = La, 50) 0.03; (Ln = Sm, 90) 1.0; (Ln = Sm + PhSiH3, 90) 2.2; (Ln = Lu, 90) 0.60; (2) (N-benzylideneaniline, Ln = Sm, 90) 0.10; (3) (N-benzylidene(trimethylsilyl)amine, Ln = Sm, 90) 0.40; (4) (N-(alpha-methylbenzylidene) (methyl)amine, Ln = Sm, 90)0.20; (5) (N-(alpha-methylbenzylidene) (benzyl)amine, Ln = Sm, 90) 0.70. The stoichiometric reaction of N-benzylidene (methyl) amine with Cp'2SmCH(SiMe3)(2) or (Cp'2SmH)(2) yields an orthometalated Cp'Sm-2-substrate complex which undergoes either hydrogenolysis/hydrogenation or competing C=N insertion of a second substrate molecule to yield a Cp'Sm-2-imine-amido complex with a seven-membered chelate ring. The stoichiometric reaction of 2-methyl-1-pyrroline with Cp'2SmCH(SiMe3)(2) or (Cp'2SmH)(2) yields a Cp'Sm-2-imine-amido complex in which two substrate molecules have been coupled to form a six-membered chelate ring (characterized by X-ray diffraction). The stoichiometric reaction of N-benzylidene(trimethylsilyl)amine with (Cp'2SmH)(2) yields a desilylated Cp'Sm-2-imine-amido complex with a four-membered Sm(NSiMe3)(CPh)N=CHPh chelate ring (characterized by X-ray diffraction). Additional heating of this product under H-2 yields S-6-symmetric (Cp'2SmCN)(6), which contains an unusual chairlike 18-membered (SmCN)(6) ring (characterized by X-ray diffraction).

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

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Language：English   Publisher：AMER CHEMICAL SOC  

Three-component coupling reaction of acid chlorides, organodisilanes, and 1,3-dienes achieves 1,4-carbosilylation of the 1,3-dienes to afford allylic silanes as the product. Bis(dibenzylideneacetone)palladium, a naked Pd(0) complex without donating ligand, showed high catalytic activity. A carbon and a silicon substituent are introduced at 1- and 4-positions of the 1,3-dienes regio- and stereoselectively with concomitant decarbonylation of the acid chlorides. A wide variety of allylic silanes are synthesized in high yields from these easily accessible substrates. On the other hand, a bully acid chloride such as adamantane-1-carboxylic acid chloride did not undergo the decarbonylation reaction but afforded allylic silanes containing acyl functionality. In all these reactions, transmetalation of the disilanes with eta(3)-allylchloropalladium intermediates might be a critical step in the catalytic cycle. As a model reaction for the transmetalation, reaction of di-mu-chlorobis[(1,2,3-eta)-4-phenyl-2-butenyl]dipalladium with disilanes was carried out. Although intermediate eta(3)-allylsilylpalladium species could not be detected, the corresponding allylic silanes, silyl chlorides, and Pd(0) metal were formed during the reaction. Furthermore, a similar three-component coupling reaction using aryl iodides, organosilylstannanes, and dienes also proceeded. However, the selectivity and the yield decreased considerably.

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

Bis-dienes 4 react with distannanes 1, disilanes 2, and silylstannanes 3 in the presence of a catalytic amount of a palladium complex to afford carbocyclization-distannylation, -disilylation and -silastannylation products in high yields. Reaction of distannanes 1a, b with bis-dienes 4a, b as well as reaction of disilane 2b with bis-diene 4d proceeded regio- and stereo-selectively to afford a single product: trans-(E),(Z) isomers. Regio- and stereo-selective reaction was also realized with the disilane 2b and bis-diene 4e to provide only trans-(E),(E) isomer. In other cases, the reactions proceeded regioselectively, but the stereoselectivity was modest. The X-ray crystal structures of the cyclopropanes 10 and 11 have been determined.

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Language：English   Publisher：AMER CHEMICAL SOC  

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Publishing type：Research paper (scientific journal)  

Bis-dienes 4 react with distannanes 1, disilanes 2, and silylstannanes 3 in the presence of a catalytic amount of a palladium complex to afford carbocyclization-distannylation, -disilylation and -silastannylation products in high yields. Reaction of distannanes 1a, b with bis-dienes 4a, b as well as reaction of disilane 2b with bis-diene 4d proceeded regio- and stereo-selectively to afford a single product: trans-(E), (Z) isomers. Regio- and stereo-selective reaction was also realized with the disilane 2b and bis-diene 4e to provide only trans-(E),(E) isomer. In other cases, the reactions proceeded regioselectively, but the stereoselectivity was modest. The X-ray crystal structures of the cyclopropanes 10 and 11 have been determined.

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Language：English   Publisher：AMER CHEMICAL SOC  

Organosilylstannanes 1 react with norbornene (2a), benzonorbornadiene (2b), and ethylene (2c) at 130-degrees-C in the presence of a catalytic amount of bis(dibenzylideneacetone)palladium combined with a trialkylphosphine to afford silylstannation products 3 in high yields.

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Language：English   Publisher：AMER CHEMICAL SOC  

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

Disilanes (1a-e) react with 1,3-dienes (2a-d) in the presence of a palladium catalyst to give dimerization-double silylation products (3a-k) regio- and stereoselectively in high yields. Pd(DBA)2 shows high catalytic activity in DMF or dioxane as the solvent at room temperature. No crossover silylations occur.

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Language：English   Publisher：AMER CHEMICAL SOC  

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Language：Japanese  

J-GLOBAL

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Language：Japanese  

J-GLOBAL

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Language：Japanese   Publisher：Kansai University  

CiNii Books

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Other Link： http://hdl.handle.net/10112/956

Language：English   Publisher：ELSEVIER SCIENCE BV  

DOI： 10.1016/j.molcata.2008.03.018

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J-GLOBAL

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J-GLOBAL

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Language：Japanese   Publishing type：Book review, literature introduction, etc.   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

Some homogeneous transition metal catalysts are highly active to cleave a-bonds between group 14 elements under mild reaction conditions. Various unsaturated compounds insert into the a-bonds to afford a wide variety of products having the group 14 elements. We have utilized silyl-stannanes (Si-Sn), disilanes (Si-Si), and distannanes (Sn-Sn) in the presence of a transition metal catalyst to realize 1,4-silylstannation of 1,3-dienes, 1,2-silylstannation of olefins, dimerization and bis-silylation of 1,3-dienes, 1,4-carbosilylation of 1,3-dienes, silylation of allylic esters, and bis-stannylation of 1,3-dienes. The structures and fluxional behavior of cis-bis(stannyl)bis(phosphine) platinum, cis-bis(silyl)bis(phosphine)platinum, and cis-bis(stannyl) bis(phosphine)palladium complexes were examined. In the fluxional process, all the spin-spin couplings are retained. The fluxionality is attributed to unimolecular twist-rotation via a pseudotetrahedral transition state.

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Language：English   Publishing type：Research paper, summary (international conference)   Publisher：AMER CHEMICAL SOC  

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Language：English   Publishing type：Research paper, summary (international conference)   Publisher：AMER CHEMICAL SOC  

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Event date： 2014.3

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Venue：Renmin University of China, Beijing, China  

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Venue：学習院大学，東京  

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Venue：学習院大学，東京  

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Venue：Hokkaido University, Sapporo  

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Venue：Hokkaido University, Sapporo  

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Venue：Hokkaido University, Sapporo  

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Venue：Hokkaido University, Sapporo  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：立命館大学びわこくさつキャンパス  

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Venue：大阪大学中之島センター  

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Venue：大阪大学中之島センター  

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Venue：大阪大学中之島センター  

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Venue：大阪大学中之島センター  

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Venue：Kuala Lumpur, Malaysia  

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Venue：Righa Royal Hotel, Kyoto  

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Venue：Rihga Royal Hotel, Kyoto  

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Venue：Rihga Royal Hotel, Kyoto  

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Venue：Rihga Royal Hotel, Kyoto  

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Event date： 2012.9

Venue：九州大学、福岡  

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Venue：九州大学、福岡  

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Venue：大阪大学  

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Venue：大阪大学、吹田  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：関西大学  

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Venue：慶応義塾大学  

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Venue：慶応義塾大学  

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Venue：慶応義塾大学  

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Venue：慶応義塾大学  

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Venue：慶応義塾大学  

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Venue：慶応義塾大学  

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Event date： 2012.3

Venue：慶応義塾大学  

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Event date： 2012.3

Venue：慶応義塾大学  

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Event date： 2012.3

Venue：慶応義塾大学  

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Event date： 2012.3

Venue：慶応義塾大学  

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Event date： 2012.3

Venue：慶応義塾大学  

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Event date： 2012.3

Venue：立命館大学びわこくさつキャンパス  

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Event date： 2012.1

Venue：Kyoto University  

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Event date： 2011.12

Venue：Nara, Japan  

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Event date： 2011.12

Venue：京都教育文化センター  

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Event date： 2011.12

Venue：京都教育文化センター  

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Event date： 2011.12

Venue：京都教育文化センター  

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Event date： 2011.12

Venue：京都教育文化センター  

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Event date： 2011.11

Venue：早稲田大学  

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Event date： 2011.11

Venue：早稲田大学  

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Event date： 2011.10

Venue：大阪科学技術センター  

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Event date： 2011.9

Venue：北見工業大学  

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Event date： 2011.9

Venue：北見工業大学  

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Event date： 2011.9

Venue：北見工業大学  

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Event date： 2011.9

Venue：中央大学  

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Event date： 2011.9

Venue：名古屋大学  

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Event date： 2011.9

Venue：名古屋大学  

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Event date： 2011.9

Venue：名古屋大学  

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Event date： 2011.9

Venue：Bangkok, Thailand  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.8

Venue：大阪府立大学  

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Event date： 2011.7

Venue：Shanghai, China  

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Event date： 2011.7

Venue：Shanghai, China  

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Event date： 2011.7

Venue：Shanghai, China  

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Event date： 2011.7

Venue：Shanghai, China  

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Event date： 2011.5

Venue：大阪大学中之島センター  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

Venue：神奈川大学  

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Event date： 2011.3

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Event date： 2011.3

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.12

Venue：Honolulu, United States  

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Event date： 2010.11

Venue：神戸国際会議場  

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Event date： 2010.11

Venue：神戸国際会議場  

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Event date： 2010.11

Venue：大阪府立大学  

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Event date： 2010.11

Venue：大阪府立大学  

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Event date： 2010.11

Venue：大阪府立大学  

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Event date： 2010.9

Venue：山梨大学  

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Event date： 2010.9

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Event date： 2010.9

Venue：中央大学  

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Event date： 2010.9

Venue：中央大学  

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Application no：特願2005-1584  Date applied：2005.1

Announcement no：特開2006-188459  Date announced：2006.7

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Application no：特願2004-253005  Date applied：2004.8

Announcement no：特開2006-69931  Date announced：2006.3

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Application no：特願2004-66597  Date applied：2004.3

Announcement no：特開2005-255564  Date announced：2995.9

Patent/Registration no：特許4402482号  Date registered：2009.11  Date issued：2009.11

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Application no：特願2004-65571  Date applied：2004.3

Announcement no：特開2005-254048  Date announced：2005.9

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Application no：PCT/JP2004/000729  Date applied：2004.1

Announcement no：WO2004/076391  Date announced：2004.9

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Application no：特願2003-300263  Date applied：2003.8

Announcement no：特開2005-68078  Date announced：2005.3

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Application no：特願平10-201554  Date applied：1998.7

Announcement no：特開2000-34351  Date announced：2000.2

Patent/Registration no：特許2963996号  Date registered：1999.8  Date issued：1999.8

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Application no：特願平10-201554  Date applied：1998.7

Announcement no：特開2000-34351  Date announced：2000.2

Patent/Registration no：特許2963996号  Date registered：1999.8  Date issued：1999.8

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Application no：PCT/US97/13560  Date applied：1997.8

Announcement no：WO98/06760  Date announced：1998.2

Patent/Registration no：United States Patent 6,040,401  Date registered：2000.3  Date issued：2000.3

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Application no：特願平4-236802  Date applied：1992.9

Announcement no：特開平6-80676  Date announced：1994.3

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Application no：特願平4-236803  Date applied：1992.9

Announcement no：特開平6-80677  Date announced：1994.3

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