Award type：Award from Japanese society, conference, symposium, etc.  Country：Japan

Award type：Award from Japanese society, conference, symposium, etc. 

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

DOI： 10.1002/anie.202302714

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

Diazulenylmethyl cations bridged with a germanium and tin moiety were synthesized. In these cations, the nature of these elements has impacts on the chemical stability and photophysical properties. Upon aggregation, these cations exhibit absorption bands in the near-infrared region, which are slightly blue-shifted compared to those of silicon-bridged congeners.

DOI： 10.1039/d3dt01491f

Open Access

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

We disclose a series of silicon-bridged diazulenylmethyl cations as stable and one-dimensionally π-extended carbocations. Connecting nonbenzenoid azulenes to a carbocation center at an appropriate position while reinforcing a planar arrangement effectively delocalizes a positive charge over the π-conjugated skeleton. This structural constraint endows the carbocations with not only high chemical stability with the pKR+ value of around 9.5, despite the absence of any electron-donating substituents, but also an intense absorption in the red region due to the effective enhancement of the transition dipole moment. X-ray crystallographic analysis revealed an offset π-stacked arrangement with the outer seven-membered ring overlapping in a face-to-face manner, in which both the steric bulk of the vertically oriented substituents on the silicon atom and the location of the counter anion should play a crucial role. Reflecting this molecular arrangement, the π-extended cations exhibited a red-shifted absorption in the near-infrared (NIR) region in both the solid state and aggregated state in solution, indicative of the formation of J-aggregates. More pronounced redshifts in the absorption band upon the formation of the aggregates were observed by proper choice of the substituents on the silicon bridge and the counter anions, and the aggregates exhibited sharp fluorescence bands with the maximum emission wavelength exceeding 800 nm. These results demonstrate the impact of the nonbenzenoid aromatic stabilization of a carbocation and the efficacy of the present design strategy for the construction of a promising π-extended cationic motif that can form NIR-absorbing and emissive J-aggregates.

DOI： 10.1021/jacs.2c08372

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

DOI： org/10.1021/jacs.2c08372

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

Abstract

Use of an iridium precatalyst with a pyridine‐based bidentate ligand allowed the efficient synthesis of benzosilole‐fused azulene derivatives via intramolecular dehydrogenative silylation of C−H bonds of azulene. Unique stimuli‐responsive fluorescence occurred upon acid treatment by appropriate fusing direction of the azulene ring. TD‐DFT calculations suggested that the major radiative decay pathway switched from S₂→S₀ to S₁→S₀ upon protonation, and the fusing mode greatly affected the degree of orbital overlap between the two related states that determine emissions of azulene.

DOI： 10.1002/ajoc.202100651

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Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ajoc.202100651

Language：English  

DOI： 10.1021/jacs.1c10680

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

DOI： 10.1246/bcsj.20210305

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Authorship：Lead author,　Corresponding author   Language：English  

Publisher：Chemical Communications  

The authors regret that the name of one of the authors (Shunsuke Moritani) was shown incorrectly in the original article. The corrected author list is as shown above. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

DOI： 10.1039/d0cc90516j

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Publishing type：Research paper (scientific journal)  

A rare example of cyclization with 5-alkynones, which possess non-polar alkynyl and less electrophilic polar keto carbonyl groups, was demonstrated. The key to promoting carbene/alkyne metathesis followed by alkylidenation with pendant CO double bonds was the Schrock-type nucleophilic reactivity of the generated chromium carbene equivalents from readily available diiodomethanes and CrCl2 by simple heating.

DOI： 10.1039/d0cc03986a

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

Treatment of 1,n-enynes with gem-dichromiomethane species prepared in situ from 1,1-diiodomethanes and CrCl2 gave alkenylbicycloalkanes. Alkenylcarbene species, which was generated via [2 + 2] cycloaddition with a triple bond, were intercepted by intramolecular cyclopropanation of a pendant double bond, and alkene metathesis did not proceed. This is a very rare example of transformation of alkynyl C≡C with gem-dimetalloalkanes. Silyl- and borylcarbene equivalents generated from gem-(dichromio)silyl- and borylmethanes promoted the coupling and cyclization of enediynes as well as 1,n-enynes.

DOI： 10.1021/acs.orglett.0c01304

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

Regioselective difunctionalization of two different C-H bonds in one pot using a three-component coupling reaction is described. The reaction order is important for controlling the reactivity and regioselectivity, and the first silylation promotes the second borylation. The introduced formyl, silyl, and boryl functional groups could be independently converted to other functional groups, and the substitution pattern for the resulting benzenes is difficult to access by conventional methods.

DOI： 10.1021/acs.orglett.9b04338

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

A (μ-aryloxo)rhenium complex was isolated and confirmed as a key precatalyst for rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes. The reaction exclusively provided ortho-alkenylphenols; the formation of para or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products was not observed. Several mechanistic experiments excluded a classical Friedel-Crafts-type mechanism, leading to the proposed phenolic hydroxyl group assisted electrophilic alkenylation as the most plausible reaction mechanism. For this purpose, the use of rhenium, a metal between the early and late transition metals in the periodic table, was key for the activation of both the soft carbon-carbon triple bond of the alkyne and the hard oxygen atom of the phenol, at the same time. ortho-Selective alkenylation with allenes also provided the corresponding adducts with a substitution pattern different from that obtained by the addition reaction with alkynes.

DOI： 10.1002/chem.201903910

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

A rhenium complex catalyzed the formation of 2-iodo-1H-indene derivatives through iodine and hydrogen migration of 3-iodopropargyl ethers. The reaction proceeded via generation of 1-iodoalkenylrhenium carbene species by sequential 1,2-iodine and 1,5-hydrogen shifts with readily available precursors under neutral conditions. The reaction mechanism and the reactivity of the generated alkenylcarbene species were also investigated.

DOI： 10.1021/acs.orglett.9b02380

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

Despite the utility of 9-silafluorenes as functional materials and as building blocks, methods for efficient functionalization of their backbone are rare, probably because of the presence of easily cleavable C-Si bonds. Although controlling the regioselectivity of iridium-catalyzed direct borylation of C-H bonds is difficult, we found that bromination and nitration of 2-methoxy-9-silafluorene under mild conditions occurred predominantly at the electron-rich position. The resulting product having methoxy and bromo groups can be utilized as a building block for the synthesis of unsymmetrically substituted 9-silafluorene-containing π-conjugated molecules.

DOI： 10.1021/acs.joc.9b00598

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

An operationally simple and direct rhenium-catalyzed ortho-alkenylation ( C-alkenylation) of unprotected phenols with alkynes was developed. The protocol provided ortho-alkenylphenols exclusively, and formation of para- or multiply alkenylated phenols and hydrophenoxylation ( O-alkenylation) products were not observed. The [3 + 2 + 1] cycloaddition of phenols and two alkynes via ortho-alkenylation was also demonstrated, in which the alkynes functioned as both two- and one-carbon units. These reactions proceeded with readily available starting materials under neutral conditions without additional ligands.

DOI： 10.1021/acs.orglett.9b01214

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

A stannyl-group-substituted gem-dichromiomethane species, generated in situ from CrCl2, TMEDA, and tributyl(diiodomethyl)stannane, worked as an efficient stannylcarbene equivalent to promote cyclopropanation of alkenes. The reaction provided synthetically useful stannylcyclopropanes directly from commercially available unactivated alkenes without using potentially flammable alkylzinc and diazo compounds. Structural characterization of stannyl- and germyl-group-substituted gem-dichromiomethane complexes and the effect of group 14 elements containing substituents for cyclopropanation are also described.

DOI： 10.1021/acs.orglett.9b00658

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

The operationally simple palladium-catalyzed double-bond migration without heteroatom-containing coordinating functional groups is described. Addition of TaCl5 as a second catalyst greatly enhanced the migration efficiency to provide β-alkylstyrenes through migration of up to a five-carbon chain. Both catalysts were commercially available, and the reaction occurred without external ligands under neutral conditions. The reaction proceeded via generation of π-allyl palladium species, which enabled the chemoselective double-bond migration of hydrocarbons in the presence of allylethers. Remote functionalization through double-bond migration was also demonstrated using FeCl3 as a second catalyst.

DOI： 10.1039/c9cc00223e

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

Combined use of oxorhenium catalysts with triphenyl phosphite as an oxygen acceptor allowed efficient deoxygenative aromatization of oxabicyclic dienes. The reaction proceeded under neutral conditions and was compatible with various functional groups. Combining this deoxygenation with regioselective bromination and trapping of the generated aryne with furan resulted in benzannulative π-extension at the periphery of the PAHs. This enabled direct use of unfunctionalized PAHs for extension of π-conjugation. Iteration of the transformations increased the number of fused-benzene rings one at a time, which has the potential to alter the properties of PAHs by fine-tuning the degree of π-conjugation, shape, and edge topology.

DOI： 10.1039/c9cc00270g

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Georg Thieme Verlag KG  

Recent advancements in unsymmetrical difunctionalization based on the substitution of two different C–H bonds in one-pot are described. Due to the difficulty of controlling reactivity and selectivity, multi-functionalization via substitution of several C–H bonds to install different functional groups has been limited until recently, in comparison with well-studied functionalization via sequential addition to unsaturated π-bonds. This difunctionalization protocol provides an efficient and rapid approach to a library of structurally complicated target molecules through the formation of multiple C–X bonds with high atom- and step-economy.

1 Introduction

2 ortho-Selective Functionalization of Two Different C–H Bonds Relative to the Directing Group

2.1 Unsymmetrical Difunctionalization with the Introduction of Similar Functional Groups

2.2 Unsymmetrical Difunctionalization with the Introduction of Different Functional Groups

2.3 ortho-Selective Unsymmetrical Difunctionalization Promoted by Two Different Directing Groups Appearing During the Progress of the Reaction

3 ortho/meta-Selective C–H Bond Difunctionalization Relative to the Directing Group

4 Sequential Difunctionalization of Fused Aromatic Compounds and Heterocycles

5 Summary and Outlook

DOI： 10.1055/s-0037-1611066

Open Access

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Publisher：Applied and Environmental Microbiology  

The Legionella Reference Center in Japan collected 427 Legionella clinical isolates between 2008 and 2016, including 7 representative isolates from corresponding outbreaks. The collection included 419 Legionella pneumophila isolates, of which 372 belonged to serogroup 1 (SG1) (87%) and the others belonged to SG2 to SG15 except for SG7 and SG11, and 8 isolates of other Legionella species (Legionella bozemanae, Legionella dumoffii, Legionella feeleii, Legionella longbeachae, Legionella londiniensis, and Legionella rubrilucens). L. pneumophila isolates were genotyped by sequence-based typing (SBT) and represented 187 sequence types (STs), of which 126 occurred in a single isolate (index of discrimination of 0.984). These STs were analyzed using minimum spanning tree analysis, resulting in the formation of 18 groups. The pattern of overall ST distribution among L. pneumophila isolates was diverse. In particular, some STs were frequently isolated and were suggested to be related to the infection sources. The major STs were ST23 (35 isolates), ST120 (20 isolates), and ST138 (16 isolates). ST23 was the most prevalent and most causative ST for outbreaks in Japan and Europe. ST138 has been observed only in Japan, where it has caused small-scale outbreaks; 81% of those strains (13 isolates) were suspected or confirmed to infect humans through bath water sources. On the other hand, 11 ST23 strains (31%) and 5 ST120 strains (25%) were suspected or confirmed to infect humans through bath water. These findings suggest that some ST strains frequently cause legionellosis in Japan and are found under different environmental conditions.

DOI： 10.1128/AEM.00721-18

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DOI： 10.1246/cl.180361

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

Amines have been identified to greatly accelerate the intermolecular anti-Markovnikov addition of carbon nucleophiles to unactivated terminal alkynes. Using a combination of [ReBr(CO)3(thf)]2 and iPr2NEt, construction of cyclic all-carbon quaternary centers was achieved with various 1,3-ketoesters, diketones, and diesters with lower catalyst loading under milder conditions. The type of addition could be easily controlled by choice of additive, highlighting the unique features of rhenium catalysis

DOI： 10.1021/acscatal.8b01338

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

An iridium-catalyzed regioselective sequential silylation and borylation of heteroarenes was developed, which represents a rare example of unsymmetrical intermolecular C−H bond difunctionalization through the introduction of two different functionalities during a one-pot transformation. Although the substrate scope for the dehydrogenative silylation of heteroarenes has been limited mainly to electron-rich five-membered rings, the current reaction proceeds with both electron-rich and electron-deficient heteroarenes with the aid of heteroatom-directing C−H bond activation. The regioselectivity of the second borylation was controlled by both steric factors and the electronic effect of the silyl group installed in the first step. In combination with the classic cross-coupling reaction, this method provides rapid access to multisubstituted heteroarenes.

DOI： 10.1002/anie.201801229

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

The combination of diiodomethylboronate ester, CrCl2 with TMEDA promoted borylcyclopropanation of unactivated alkenes under mild conditions. Compared with the typical Simmons-Smith cyclopropanation, the current protocol offers the following advantages: (1) the reaction proceeds stereoselectively with disubstituted alkenes even without hydroxy or alkoxy groups; (2) both electron-rich and electron-deficient alkenes can be applicable; and (3) the reaction does not require potentially flammable alkylzinc. These unique reactivity features result from the steric and electronic nature of the gem-dichromiomethane intermediates.

DOI： 10.1021/acs.orglett.7b02956

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

Azulene-fused polycyclic aromatic hydrocarbons (PAHs) were synthesized from commercially available azulene in four steps. The resulting azulene conjugates exhibited significantly narrow HOMO-LUMO bandgaps with high air. stability, confirmed by photophysical study. Introduction 1; of azulene also enabled the unique reversible stimuli-responsiveness even with the weak acid and base, which can potentially control the,degree of conjugation and optoelectronic properties-by simple acid base and redox processes.

DOI： 10.1021/acs.orglett.7b02729

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

Stabilization by a silyl group on the methylene carbon and a diamine ligand led to the isolation of gem-dichromiomethane species. X-ray crystallography confirmed the identity of the structure of this rare example of reactive gem-dimetalloalkane species. The isolated gem-dichromiomethane complex acted as a storable silylmethylidene carbene equivalent, with reactivity that could be changed dramatically upon addition of a Lewis acid (ZnCl2) and a base (TMEDA) to promote both silylalkylidenation of polar aldehydes and silylcyclopropanation of nonpolar alkenes. Identification of a key reactive species also identified the catalytic version of these transformations and provided insights into the reaction mechanism. In contrast to Simmons-Smith cyclopropanation, the real reactive species for the current cyclopropanation was a chromiocarbene species, not a chromium carbenoid species.

DOI： 10.1021/jacs.7b07487

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DOI： 10.1002/chem.201701579

PubMed

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

While cyclopropanes have been explored as synthetically valuable building blocks, their transformation without conjugated substituents or directly substituted heteroatoms remains challenging. The current study describes the iridium-catalysed ring-opening hydrosilylation of cyclopropanes. A nitrogen-based directing group was found to control the reactivity of iridium active species as well as the regiochemistry of carbon-carbon bond cleavage and hydrosilylation.

DOI： 10.1039/c7cc04296e

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

Stoichiometric amounts of oxidants are widely used as promoters (hydrogen acceptors) in dehydrogenative silylation of C-H bonds. However, the present study demonstrates that silylative and germylative cyclization with dehydrogenation can proceed efficiently, even without hydrogen acceptors. The combination of [RhCl(cod)](2) and PPh3 was effective for both transformations, and allowed a reduction in reaction temperature compared with our previous report. Monitoring of the reactions revealed that both transformations had an induction period for the early stage, and that the rate constant of dehydrogenative germylation was greater than that of dehydrogenative silylation. Competitive reactions in the presence of 3,3-dimethyl-1-butene indicated that the ratio of dehydrogenative metalation and hydrometalation was affected by reaction temperature when a hydrosilane or hydrogermane precursor was used. Further mechanistic insights of oxidant-free dehydrogenative silylation, including the origin of these unique reactivities, were obtained by density functional theory studies.

DOI： 10.1002/chem.201701579

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

Dehydrogenative dimerization of benzylmethylsilanes under iridium catalysis via site-selective sequential silylations of a C(sp(3))-H bond of the methyl group and ortho C(sp(2))-H bond of the benzyl group is described. Silicon-containing heterocycles were obtained in a single step from readily available functionalized benzylmethylsilanes.

DOI： 10.1246/cl.170369

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

A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon-carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon-heteroatom bonds as well as nonpolar carbon-carbon unsaturated pi bonds.

DOI： 10.1002/anie.201701159

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

DOI： 10.1002/0471264229.os094.20

Total pages：1  

Total pages：1   Responsible for pages：61-62   Language：Japanese

Total pages：3   Language：English

Language：English   Publisher：AMER CHEMICAL SOC  

Stabilization by a silyl group on the methylene carbon and a diamine ligand led to the isolation of gem-dichromiomethane species. X-ray crystallography confirmed the identity of the structure of this rare example of reactive gem-dimetalloalkane species. The isolated gem-dichromiomethane complex acted as a storable silylmethylidene carbene equivalent, with reactivity that could be changed dramatically upon addition of a Lewis acid (ZnCl2) and a base (TMEDA) to promote both silylalkylidenation of polar aldehydes and silylcyclopropanation of nonpolar alkenes. Identification of a key reactive species also identified the catalytic version of these transformations and provided insights into the reaction mechanism. In contrast to Simmons-Smith cyclopropanation, the real reactive species for the current cyclopropanation was a chromiocarbene species, not a chromium carbenoid species.

DOI： 10.1021/jacs.7b07487

Web of Science

Language：English   Publisher：ROYAL SOC CHEMISTRY  

While cyclopropanes have been explored as synthetically valuable building blocks, their transformation without conjugated substituents or directly substituted heteroatoms remains challenging. The current study describes the iridium-catalysed ring-opening hydrosilylation of cyclopropanes. A nitrogen-based directing group was found to control the reactivity of iridium active species as well as the regiochemistry of carbon-carbon bond cleavage and hydrosilylation.

DOI： 10.1039/c7cc04296e

Web of Science

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

Stoichiometric amounts of oxidants are widely used as promoters (hydrogen acceptors) in dehydrogenative silylation of C-H bonds. However, the present study demonstrates that silylative and germylative cyclization with dehydrogenation can proceed efficiently, even without hydrogen acceptors. The combination of [RhCl(cod)](2) and PPh3 was effective for both transformations, and allowed a reduction in reaction temperature compared with our previous report. Monitoring of the reactions revealed that both transformations had an induction period for the early stage, and that the rate constant of dehydrogenative germylation was greater than that of dehydrogenative silylation. Competitive reactions in the presence of 3,3-dimethyl-1-butene indicated that the ratio of dehydrogenative metalation and hydrometalation was affected by reaction temperature when a hydrosilane or hydrogermane precursor was used. Further mechanistic insights of oxidant-free dehydrogenative silylation, including the origin of these unique reactivities, were obtained by density functional theory studies.

DOI： 10.1002/chem.201701579

Web of Science

Language：English   Publisher：CHEMICAL SOC JAPAN  

Dehydrogenative dimerization of benzylmethylsilanes under iridium catalysis via site-selective sequential silylations of a C(sp(3))-H bond of the methyl group and ortho C(sp(2))-H bond of the benzyl group is described. Silicon-containing heterocycles were obtained in a single step from readily available functionalized benzylmethylsilanes.

DOI： 10.1246/cl.170369

Web of Science

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

A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon-carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon-heteroatom bonds as well as nonpolar carbon-carbon unsaturated pi bonds.

DOI： 10.1002/anie.201701159

Web of Science

DOI： 10.15227/orgsyn.094.0280

Event date： 2023.12

Language：English   Presentation type：Oral presentation (invited, special)  

Country：Japan  

Event date： 2023.11

Language：English   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2023.10

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：名古屋   Country：Japan  

Event date： 2023.10

Language：Japanese   Presentation type：Public lecture, seminar, tutorial, course, or other speech  

Venue：東京   Country：Japan  

Event date： 2023.6

Language：English   Presentation type：Oral presentation (general)  

Venue：Raleigh, North Carolina   Country：United States  

Application no：特願2014-47900 

Patent/Registration no：特許Jpn. Kokai Tokkyo Koho (2015), JP 2015-172009 A 20151001 

Application no：特願Jpn. Kokai Tokkyo Koho (2018), JP 2018-209329