Award type：International academic award (Japan or overseas) 

Country：Japan

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

The Pd-catalyzed desulfonative cross-coupling reaction of benzylic sulfone derivatives with 1,3-oxazoles via a deprotonative pathway has been developed. Broad substrate scope for both sulfone and 1,3-oxazole partners is observed, affording a variety of 1,3-oxazole-containing triarylmethanes. Sulfone partners that are primary benzylic, secondary benzylic, and benzhydryl are all effective. Using this method, the straightforward synthesis of multiply arylated structures has been demonstrated.

DOI： 10.1021/acs.orglett.7b01510

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PubMed

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

The development of fluorinated sulfone derivatives as versatile electrophiles for Suzuki Miyaura cross-coupling reactions is described. Introducing electron-withdrawing groups on the aryl ring of the sulfone facilitates the Pd-catalyzed activation of C-SO2 bonds. Cross-coupling reactions with fluorinated sulfone electrophiles are reported, leading to a variety of multiply arylated products in good yields. The reactivity of this unusual electrophile is benchmarked versus common electrophiles and its use in iterative cross-couplings for concise synthesis of biologically active molecules is described.

DOI： 10.1021/acscatal.6b03434

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

Cell proliferation is crucial to the growth of multicellular organisms, and thus the proper control of cell division is important to prevent developmental arrest or overgrowth. Nevertheless, tools for controlling cell proliferation are still poor in plant. To develop novel tools, we focused on a specific compound family, triarylmethanes, whose members show various antiproliferative activities in animals. By combining organic chemistry to create novel and diverse compounds containing the triarylmethyl moiety and biological screens based on live-cell imaging of a fluorescently labeled tobacco Bright Yellow-2 (BY-2) culture cell line (Nicotiana tabacum), we isolated (3-furyl)diphenylmethane as a strong but partially reversible inhibitor of plant cell division. We also found that this agent had efficient antiproliferative activity in developing organs of Arabidopsis thaliana without causing secondary defects in cell morphology, and induced rapid cell division arrest independent of the cell cycle stage. Given that (3-furyl)diphenylmethane did not affect the growth of a human cell line (HeLa) and a budding yeast (Saccharomyces cerevisiae), it should act specifically on plants. Taking our results together, we propose that the combination of desired chemical synthesis and detailed biological analysis is an effective tool to create novel drugs, and that (3-furyl)diphenylmethane is a specific antiproliferative agent for plants.

DOI： 10.1093/pcp/pcw140

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

Triarylmethanes and related compounds are fascinating molecules because of their structural and physical properties, many potential applications in organic functional materials, and high biological activity. Recently, catalysis has provided new synthesis routes to triarylmethanes with high selectivity and diversity, including the possibility of preparing enantiomerically enriched derivatives, which is typically challenging using classical methods. This Perspective reviews recent advances in new synthesis approaches to triarylmethanes using well-defined catalysts. These methods will allow the development of new, unexplored triarylmethane structures.

DOI： 10.1021/acscatal.5b00909

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

The selective synthesis of multiarylated acetonitriles via sequential palladium-catalyzed arylations of chloroacetonitrile is reported. The three aryl groups are installed via a Pd-catalyzed Suzuki-Miyaura cross coupling reaction followed by back-to-back C-H arylations to afford triarylacetonitriles in three steps with no over-arylation at any step. The triarylacetonitrile products can be converted into highly functionalized species including tetraarylmethanes. This new strategy provides rapid access to a variety of unsymmetrical tri- and tetraarylmethane derivatives from simple, readily available starting materials.

DOI： 10.1021/ol503213z

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

DOI： 10.1139/cjc-2022-0271

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

DOI： 10.1055/a-1942-5695

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

DOI： 10.1021/acscatal.2c02233

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

DOI： 10.1021/jacsau.2c00004

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

DOI： 10.1021/acscatal.1c05608

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

DOI： 10.1021/jacs.1c11857

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

DOI： 10.1002/tcr.202100210

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Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/tcr.202100210

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

DOI： 10.1021/acs.orglett.1c01892

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

<p>A series of chiral Au₁₃ nanoclusters were synthesized <italic>via</italic> the direct reduction of achiral dinuclear Au(<sc>i</sc>) halide complexes ligated by <italic>ortho</italic>-xylyl-linked bis-<italic>N</italic>-heterocyclic carbene (NHC) ligands.</p>

DOI： 10.1039/d1sc03076k

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/d0cc01482f

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media {LLC}  

DOI： 10.1038/s41467-019-11758-w

PubMed

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/c9ob01099h

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PubMed

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

© 2019, The Author(s), under exclusive licence to Springer Nature Limited. Magic-number gold nanoclusters are atomically precise nanomaterials that have enabled unprecedented insight into structure–property relationships in nanoscience. Thiolates are the most common ligand, binding to the cluster via a staple motif in which only central gold atoms are in the metallic state. The lack of other strongly bound ligands for nanoclusters with different bonding modes has been a significant limitation in the field. Here, we report a previously unknown ligand for gold(0) nanoclusters—N-heterocyclic carbenes (NHCs)—which feature a robust metal–carbon single bond and impart high stability to the corresponding gold cluster. The addition of a single NHC to gold nanoclusters results in significantly improved stability and catalytic properties in the electrocatalytic reduction of CO 2 . By varying the conditions, nature and number of equivalents of the NHC, predominantly or exclusively monosubstituted NHC-functionalized clusters result. Clusters can also be obtained with up to five NHCs, as a mixture of species.

DOI： 10.1038/s41557-019-0246-5

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

DOI： 10.1002/chem.201805638

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

Highly stable gold nanoparticles (Au NPs) functionalized by bidentate N-heterocyclic carbene (NHC) ligands have been synthesized by top-down and bottom-up approaches. A detailed study of the effect of alkylation, denticity, and method of synthesis has led to the production of NHC-stabilized nanoparticles with higher thermal stability than bi- and tridentate thiol-protected Au NPs and than monodentate NHC-stabilized NPs. Importantly, bidentate NHC-protected NPs also displayed unprecedented stability to external thiol, which has been an unsolved problem to date with all nanoparticles. Thus, multidentate NHC ligands are an important, and as yet unrecognized, step forward for the preparation of high stability nanomaterials.

DOI： 10.1021/jacs.7b08516

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PubMed

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

NHC-Au-I complexes were used to prepare stable, water-soluble, NHC-protected gold nanoparticles. The water-soluble, charged nature of the nanoparticles permitted analysis by polyacrylamide gel electrophoresis (PAGE), which showed that the nanoparticles were highly monodisperse, with tunable core diameters between 2.0 and 3.3 nm depending on the synthesis conditions. Temporal, thermal, and chemical stability of the nanoparticles were determined to be high. Treatment with thiols caused etching of the particles after 24 h; however larger plasmonic particles showed greater resistance to thiol treatment. These water-soluble, bio-compatible nanoparticles are promising candidates for use in photoacoustic imaging, with even the smallest nanoparticles giving reliable photoacoustic signals.

DOI： 10.1002/anie.201701605

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

A scandium-triflate-catalyzed arylative desulfonation of diarylmethyl phenyl sulfones with arenes and heteroarenes was established. A variety of both sulfone and arene substrates were reacted to afford symmetric and nonsymmetric triarylmethanes in good yields. Further transformations of the resulting triarylmethanes and application to the concise synthesis of a bactericidal agent analogue were also demonstrated.

DOI： 10.1021/acs.orglett.6b00744

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：NATURE PUBLISHING GROUP  

The Suzuki-Miyaura cross-coupling is one of the most often utilized reactions in the synthesis of pharmaceutical compounds and conjugated materials. In its most common form, the reaction joins two sp(2)-functionalized carbon atoms to make a biaryl or diene/polyene unit. These substructures are widely found in natural products and small molecules and thus the Suzuki-Miyaura cross-coupling has been proposed as the key reaction for the automated assembly of such molecules, using protecting group chemistry to affect iterative coupling. We present herein, a significant advance in this approach, in which multiply functionalized cross-coupling partners can be employed in iterative coupling without the use of protecting groups. To accomplish this, the orthogonal reactivity of different boron substituents towards the boron-to-palladium transmetalation reaction is exploited. The approach is illustrated in the preparation of chiral enantioenriched compounds, which are known to be privileged structures in active pharmaceutical compounds.

DOI： 10.1038/ncomms11065

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

DOI： 10.1002/anie.201307019

PubMed

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

Triarylmethanes, which are valuable structures in materials, sensing and pharmaceuticals, have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. This method provides a new synthetic approach to multisubstituted triarylmethanes using readily available haloarenes and aryl boronic acids, and is also valuable for the preparation of unexplored triarylmethane-based materials and pharmaceuticals.

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

Triarylmethanes, which are valuable structures in materials, sensing and pharmaceuticals, have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. This method provides a new synthetic approach to multisubstituted triarylmethanes using readily available haloarenes and aryl boronic acids, and is also valuable for the preparation of unexplored triarylmethane-based materials and pharmaceuticals.

DOI： 10.1002/anie.201307019

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

We have established a unique Pd-catalyzed tetraallylation of C-60 with allyl chloride and allylstannane that likely proceeds by the action of amphiphilic bis(pi-ally)palladium. Mechanistic analysis has revealed that both steric (for the first diallylation) and electronic (for the second diallylation) factors are responsible for high regioselectivity. The ring-closing metathesis reaction and hydrogenation of the tetraallylated product took place in the presence of Ru and Rh catalysts. Moreover, we found that chiral phosphoramidites are effective chiral ligands for the enantioselective tetraallylation of C-60. Pronounced enantioselectivity up to 88% ee was realized in the production of tetraallylated C-60.

DOI： 10.1039/c2sc21126b

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

An aziridine moiety on the fullerene core can serve as an acid-triggered reacting template for the controlled synthesis of a range of functionalized fullerenes that are otherwise difficult to synthesize in an efficient and selective manner. A copper-catalyzed aziridination of C-60 for the practical synthesis of aziridinofullerene 1 and acid-catalyzed reactions of 1 with mono- and bifunctional nucleophiles as well as alkynes are described. The rapid generation of structural diversity in a single chemical operation using the common platform 1 is notable.

DOI： 10.1021/ja111213k

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

A Rh-catalyzed reaction of C-60 and C-70 with organoboron compounds is described. This new catalytic method enables introduction of various organic groups onto C-60 and C-70. [Rh-(cod) (MeCN)(2)]BF4 proved to be the most effective catalyst in terms of productivity and selectivity. The reaction generally proceeds with a high regioselectivity and in a mono-addition selective manner. It was found that water is an essential additive to promote the reaction. By X-ray crystal structure analysis, we have confirmed the reaction site of organometallic-based hydroarylation of C-70 for the first time. Various functional fullerenes, such as fullerene-tagged amino acids and fullerene-capped pi systems, can be synthesized. The X-ray crystal structure of biphenyl-attached C-60 revealed an interesting opportunity for the well-organized alignment of bucky balls by taking advantage of CH-pi interactions.

DOI： 10.1002/asia.201000583

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

A Pd-catalyzed tetraallylation of C-60 that selectively occurs with an unsymmetrical addition pattern has been established. Treatment of C-60 with CH2=CHCH2Cl, CH2=CHCH2SnBu3, and PdCl2[P(OPh)(3)](2) in 1,2-Cl2C6H4 at 50 degrees C afforded the tetraallylated fullerene in 74% yield with virtually complete regioselectivity. Mechanistic investigations showed that (i) tetraallylation proceeds through consecutive nucleophilic/electrophilic allylations [Likely via a bis(pi-allyl)palladium intermediate] and (ii) both steric (for the first diallylation) and electronic (for the second diallylation) factors are responsible for the high regioselectivity.

DOI： 10.1021/ja9071173

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

DOI： 10.1002/chem.200900022

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Bentham Science Publishers B.V.  

It was postulated that N6-allyl bicyclic derivatives 1 bind with N-8 at the proton donor site of the σ1 receptor and that a substituent in 2-position of the bicyclic framework 1 results in unfavorable steric interactions with the σ1 receptor protein. In order to support this hypothesis both enantiomers of 6-allyl-8-(4-methoxybenzyl)-6,8- diazabicyclo[3.2.2]non-2-ene (2/ent-2) and 6-benzyl-8-(4-methoxybenzyl)-6,8- diazabicyclo[3.2.2]nonane 3/ent-3 were synthesized stereoselectively. The (S,S)-configured enantiomers 2 and 3 are the eutomers with eudismic ratios of 31 and 4.8, respectively. Therefore, these enantiomers are used in the σ1 pharmacophore model. The N6-allyl derivative 2 with a double bond in the three carbon bridge adopts the orientation 2c with N-8 interacting with the σ1 receptor proton donor site (Fig. 2) resulting in slightly reduced steric interactions of the small double bond in 2/3-position. The almost C2-symmetric benzyl derivative 3 can adopt both orientations 2c and 2d at the σ1 receptor (N-8 or N-6 interacts with the σ1 receptor proton donor site) resulting in subnanomolar σ1 receptor affinity (Ki = 0.91 nM). © 2009 Bentham Science Publishers Ltd.

DOI： 10.2174/1871524910909030220

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Other Link： http://orcid.org/0000-0003-0153-3178

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

A Pd(II) catalyst for the hydroarylation of fullerene with boronic acids is presented. Treatment of C(60) with an arylboronic acid in the presence of a catalytic amount of Pd(2-PyCH=NPh)(OCOC(6)F(5))(2) in H(2)O/1,2-Cl(2)C(6)H(4) at room temperature furnishes the hydroarylation product (Ar-C(60)-H) in good yield with high selectivity. This complex possesses high catalytic activity paired with bench stability in the solid state.

DOI： 10.1021/ol801936j

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

A new organoboron-based arylation and alkenylation of C-60 catalyzed by a rhodium complex was developed. A treatment of C-60 with an organoboron compound in the presence of a catalytic amount of [Rh(cod)(CH3CN)(2)]BF4 in H2O/1,2-Cl2C6H4 furnished a functionalized fullerene (R-C-60-H) with good to excellent selectivity. Aryl, heteroaryl, and alkenyl groups can be installed by the reactions using the corresponding boronic acids, pinacol esters, and potassium trifluoroborates.

DOI： 10.1021/ja073042x

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Application no：特願PCT/JP2014/078653