Updated on 2022/04/12

写真a

 
MURAI Masahito
 
Organization
Graduate School of Science Associate professor
Graduate School
Graduate School of Science
Undergraduate School
School of Science Department of Chemistry
Title
Associate professor

Degree 1

  1. 博士(工学) ( 2010.3   京都大学 ) 

Research Interests 2

  1. Synthetic Organic Chemistry

  2. 有機金属化学

Research Areas 3

  1. Others / Others  / 有機金属化学

  2. Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

  3. Nanotechnology/Materials / Functional solid state chemistry

Current Research Project and SDGs 1

  1. Catalytic direct functionalization of hydrocarbons with high atomic efficiency

Research History 4

  1. Nagoya University   Associate professor

    2018.4

  2. Okayama University   Assistant Professor

    2012.10 - 2018.3

  3. Japan Society for Promotion of Science   Researcher

    2011.6 - 2012.6

  4. Tokyo Institute of Technology   Researcher

    2010.4 - 2012.9

Education 2

  1. Kyoto University

    2005.4 - 2010.3

  2. Kyoto University

    2001.4 - 2005.3

Professional Memberships 5

  1. 日本化学会

  2. 近畿化学協会

  3. 有機合成化学協会

  4. American Chemical Society

  5. 基礎有機化学会

Committee Memberships 1

  1. 日本化学会東海支部   幹事  

    2020.4 - 2022.3   

Awards 6

  1. 第67回日本化学会進歩賞

    2018.3   日本化学会   金属活性種の設計に基づく炭化水素への直截的な官能基導入法の開発

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

  2. Thieme Chemistry Journals Award 2022

    2022.1   Thieme Chemistry  

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    Award type:International academic award (Japan or overseas)  Country:Germany

  3. Chemist Award BCA 2021

    2021.12  

    Masahito Murai

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    Award type:Award from publisher, newspaper, foundation, etc.  Country:Japan

  4. 日本化学会 若い世代の特別講演証

    2016.3   日本化学会  

    村井征史

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

  5. 日本化学会春季年会 優秀講演賞(学術)

    2015.3   日本化学会  

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

  6. 有機合成化学協会ADEKA研究企画賞

    2013.12   有機合成化学協会  

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Papers 27

  1. Silylative Cyclization with Dehydrogenation Leading to Benzosilole-Fused Azulenes Showing Unique Stimuli-Responsive Fluorescence

    Murai M.

    Asian Journal of Organic Chemistry   Vol. 11 ( 1 )   2022.1

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    Language:Japanese   Publisher:Asian Journal of Organic Chemistry  

    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

    Scopus

  2. Correction to "Isolation and Structural Characterization of <i>Geminal</i> Di(iodozincio)methane Complexes Stabilized with Nitrogen Ligands".

    Nishida Y, Hosokawa N, Murai M, Takai K

    Journal of the American Chemical Society   Vol. 143 ( 48 ) page: 20524   2021.12

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    Language:English  

    DOI: 10.1021/jacs.1c10680

    PubMed

  3. Intramolecular Silylative Cyclization with Dehydrogenation Leading to Benzosilole-Fused Azulenes with Unique Stimuli-Responsiveness Reviewed

    Masahito Murai

    Asian Journal of Organic Chemistry     2021.11

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    Authorship:Lead author, Corresponding author   Language:English  

  4. Regiodivergent Carbene/Alkyne Metathesis in Chromium-Mediated Coupling and Cyclization with 1,6-Enynes Reviewed

    Masahito Murai, Ryuji Taniguchi, Kazuhiko Takai

    Bulletin of the Chemical Society of Japan     2021.10

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

    DOI: 10.1246/bcsj.20210305

  5. Cyclization of 5-alkynones with chromium alkylidene equivalents generatedin situfromgem-dichromiomethanes

    Murai Masahito, Taniguchi Ryuji, Kurogi Takashi, Shunsuke Moritani, Takai Kazuhiko

    CHEMICAL COMMUNICATIONS   Vol. 56 ( 67 ) page: 9711 - 9714   2020.8

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    Publisher:Chemical Communications  

    DOI: 10.1039/d0cc03986a

    Web of Science

    Scopus

    PubMed

  6. Cyclization of 1,n-Enynes Initiated by the Addition Reaction of gem-Dichromiomethane Reagents to Alkynes

    Murai Masahito, Taniguchi Ryuji, Takai Kazuhiko

    ORGANIC LETTERS   Vol. 22 ( 10 ) page: 3985 - 3988   2020.5

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  7. Regioselective Sequential Silylation and Borylation of Aromatic Aldimines as a Strategy for Programming Synthesis of Multifunctionalized Benzene Derivatives

    Murai Masahito, Nishinaka Naoki, Enoki Takahiro, Takai Kazuhiko

    ORGANIC LETTERS   Vol. 22 ( 1 ) page: 316 - 321   2020.1

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  8. Mechanistic Insights into Rhenium-Catalyzed Regioselective C-Alkenylation of Phenols with Internal Alkynes

    Murai Masahito, Yamamoto Masaki, Takai Kazuhiko

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 25 ( 66 ) page: 15189 - 15197   2019.11

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    Publisher:Chemistry - A European Journal  

    DOI: 10.1002/chem.201903910

    Web of Science

    Scopus

    PubMed

  9. Rhenium-Catalyzed Cyclization via 1,2-Iodine and 1,5-Hydrogen Migration for the Synthesis of 2-lodo-1H-indenes

    Murai Masahito, Takai Kazuhiko

    ORGANIC LETTERS   Vol. 21 ( 17 ) page: 6756 - 6760   2019.9

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  10. Regioselective Functionalization of 9,9-Dimethyl-9-silafluorenes by Borylation, Bromination, and Nitration.

    Murai M, Nishinaka N, Kimura M, Takai K

    The Journal of organic chemistry   Vol. 84 ( 9 ) page: 5667 - 5676   2019.5

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  11. Rhenium-Catalyzed Regioselective ortho-Alkenylation and [3 + 2 + 1] Cycloaddition of Phenols with Internal Alkynes.

    Murai M, Yamamoto M, Takai K

    Organic letters   Vol. 21 ( 9 ) page: 3441 - 3445   2019.5

  12. Chromium-Mediated Stannylcyclopropanation of Alkenes with (Diiodomethyl)stannanes.

    Murai M, Taniguchi R, Mizuta C, Takai K

    Organic letters   Vol. 21 ( 8 ) page: 2668 - 2672   2019.4

  13. Palladium-catalyzed double-bond migration of unsaturated hydrocarbons accelerated by tantalum chloride.

    Murai M, Nishimura K, Takai K

    Chemical communications (Cambridge, England)   Vol. 55 ( 19 ) page: 2769 - 2772   2019.2

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  14. Regioselective arene homologation through rhenium-catalyzed deoxygenative aromatization of 7-oxabicyclo[2.2.1]hepta-2,5-dienes.

    Murai M, Ogita T, Takai K

    Chemical communications (Cambridge, England)   Vol. 55 ( 16 ) page: 2332 - 2335   2019.2

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  15. Unsymmetrical Difunctionalization of Two Different C-H Bonds in One Pot Under Transition-Metal Catalysis

    Murai Masahito, Takai Kazuhiko

    SYNTHESIS-STUTTGART   Vol. 51 ( 1 ) page: 40 - 54   2019.1

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    Language:Japanese  

    DOI: 10.1055/s-0037-1611066

    Web of Science

  16. Catalytic Cleavage and Reformation of Ethereal sigma-Bonds Reviewed

    Murai Masahito, Origuchi Kazuki, Takai Kazuhiko

    CHEMISTRY LETTERS   Vol. 47 ( 7 ) page: 927 - 930   2018.7

  17. Amine-Promoted anti-Markovnikov Addition of 1,3-Dicarbonyl Compounds with Terminal Alkynes under Rhenium Catalysis Reviewed

    Masahito Murai, Erika Uemura, Kazuhiko Takai

    ACS Catalysis   Vol. 8 ( 6 ) page: 5454 - 5459   2018.6

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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

    Web of Science

    Scopus

  18. Iridium-Catalyzed Sequential Silylation and Borylation of Heteroarenes Based on Regioselective C−H Bond Activation Reviewed

    Masahito Murai, Naoki Nishinaka, Kazuhiko Takai

    Angewandte Chemie - International Edition   Vol. 57 ( 20 ) page: 5843 - 5847   2018.5

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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

    Web of Science

    Scopus

  19. Synthesis of Borylcyclopropanes by Chromium-Promoted Cyclopropanation of Unactivated Alkenes.

    Murai M, Mizuta C, Taniguchi R, Takai K

    Organic letters   Vol. 19 ( 22 ) page: 6104 - 6107   2017.11

  20. Azulene-Fused Linear Polycyclic Aromatic Hydrocarbons with Small Bandgap, High Stability, and Reversible Stimuli Responsiveness.

    Murai M, Iba S, Ota H, Takai K

    Organic letters   Vol. 19 ( 20 ) page: 5585 - 5588   2017.10

  21. Structural Characterization and Unique Catalytic Performance of Silyl-Group-Substituted Geminal Dichromiomethane Complexes Stabilized with a Diamine Ligand Reviewed

    Masahito Murai, Ryuji Taniguchi, Naoki Hosokawa, Yusuke Nishida, Hiroko Mimachi, Toshiyuki Oshiki, Kazuhiko Takai

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 139 ( 37 ) page: 13184 - 13192   2017.9

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    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

    Web of Science

    PubMed

  22. Iridium-catalysed hydrosilylation of cyclopropanes via regioselective carbon-carbon bond cleavage.

    Murai M, Nishiyama A, Nishinaka N, Morita H, Takai K

    Chemical communications (Cambridge, England)   Vol. 53 ( 66 ) page: 9281 - 9284   2017.8

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  23. Rhodium-Catalyzed Silylative and Germylative Cyclization with Dehydrogenation Leading to 9-Sila- and 9-Germafluorenes: A Combined Experimental and Computational Mechanistic Study.

    Murai M, Okada R, Asako S, Takai K

    Chemistry (Weinheim an der Bergstrasse, Germany)   Vol. 23 ( 45 ) page: 10861 - 10870   2017.8

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  24. Rhodium-Catalyzed Silylative and Germylative Cyclization with Dehydrogenation Leading to 9-Sila- and 9-Germafluorenes: A Combined Experimental and Computational Mechanistic Study Reviewed

    Masahito Murai, Ryo Okada, Sobi Asako, Kazuhiko Takai

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 23 ( 45 ) page: 10861 - 10870   2017.8

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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

    Web of Science

  25. Iridium-catalyzed Dehydrogenative Dimerization of Benzylmethylsilanes via Silylation of C(sp(3))-H Bonds Adjacent to a Silicon Atom Reviewed

    Masahito Murai, Yutaro Takeuchi, Kazuhiko Takai

    CHEMISTRY LETTERS   Vol. 46 ( 7 ) page: 1044 - 1047   2017.7

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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

    Web of Science

  26. Rhenium-Catalyzed Construction of Polycyclic Hydrocarbon Frameworks by a Unique Cyclization of 1,n-Diynes Initiated by 1,1-Difunctionalization with Carbon Nucleophiles.

    Murai M, Uemura E, Hori S, Takai K

    Angewandte Chemie (International ed. in English)   Vol. 56 ( 21 ) page: 5862 - 5866   2017.5

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  27. Rhenium-Catalyzed ortho-Alkylation of Phenols Reviewed

    Yoichiro Kuninobu, Masaki Yamamoto, Mitsumi Nishi, Tomoyuki Yamamoto, Takashi Matsuki, Masahito Murai, Kazuhiko Takai

    Organic Synthses   Vol. 94   page: 280 - 291   2017

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

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Books 4

  1. 多環芳香族炭化水素の効率的な機能化法の開発

    村井征史( Role: Sole author)

    日本化学会  2016 

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    Total pages:2   Responsible for pages:981-982   Language:Japanese

  2. 電子供与性配位子としてのカルボジカルベンの化学

    村井征史( Role: Sole author)

    近畿化学協会 有機金属部会  2015 

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    Total pages:1  

  3. 元素の個性の再探求による新反応の確立と新物質の創製

    村井征史( Role: Sole author)

    化学同人  2015 

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

  4. Photoinitated click reactions for the creation of spatially defined materials

    Daigo Miyajima, Mmasahito Murai, Craig J. Hawker( Role: Joint author)

    高分子学会  2012 

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    Total pages:3   Language:English

MISC 11

  1. Amine-Promoted anti-Markovnikov Addition of 1,3-Dicarbonyl Compounds with Terminal Alkynes under Rhenium Catalysis

    Masahito Murai, Erika Uemura, Kazuhiko Takai

    ACS Catalysis   Vol. 8 ( 6 ) page: 5454 - 5459   2018.6

     More details

    Language:English   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

    Scopus

  2. Iridium-Catalyzed Sequential Silylation and Borylation of Heteroarenes Based on Regioselective C−H Bond Activation

    Masahito Murai, Naoki Nishinaka, Kazuhiko Takai

    Angewandte Chemie - International Edition   Vol. 57 ( 20 ) page: 5843 - 5847   2018.5

     More details

    Language:English   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

    Scopus

  3. Catalytic Cleavage and Reformation of Ethereal sigma-Bonds(共著)

    Masahito Murai, Kazuki Origuchi, Kazuhiko Takai

    Chemistry Letters   Vol. 47   page: 927 - 930   2018

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  4. Synthesis of Borylcyclopropanes by Chromium-Promoted Cyclopropanation of Unactivated Alkenes

    Masahito Murai, Chisato Mizuta, Ryuji Taniguchi, Kazuhiko Takai

    ORGANIC LETTERS   Vol. 19 ( 22 ) page: 6104 - 6107   2017.11

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    Language:English   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

    Web of Science

  5. Azulene-Fused Linear Polycyclic Aromatic Hydrocarbons with Small Bandgap, High Stability, and Reversible Stimuli Responsiveness

    Masahito Murai, Shinji Iba, Hiromi Ota, Kazuhiko Takai

    ORGANIC LETTERS   Vol. 19 ( 20 ) page: 5585 - 5588   2017.10

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    Language:English   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

    Web of Science

  6. Iridium-catalysed hydrosilylation of cyclopropanes via regioselective carbon-carbon bond cleavage

    Masahito Murai, Atsushi Nishiyama, Naoki Nishinaka, Haruka Morita, Kazuhiko Takai

    CHEMICAL COMMUNICATIONS   Vol. 53 ( 66 ) page: 9281 - 9284   2017.8

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    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

  7. Rhodium-Catalyzed Silylative and Germylative Cyclization with Dehydrogenation Leading to 9-Sila- and 9-Germafluorenes: A Combined Experimental and Computational Mechanistic Study

    Masahito Murai, Ryo Okada, Sobi Asako, Kazuhiko Takai

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 23 ( 45 ) page: 10861 - 10870   2017.8

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    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

  8. Iridium-catalyzed Dehydrogenative Dimerization of Benzylmethylsilanes via Silylation of C(sp(3))-H Bonds Adjacent to a Silicon Atom

    Masahito Murai, Yutaro Takeuchi, Kazuhiko Takai

    CHEMISTRY LETTERS   Vol. 46 ( 7 ) page: 1044 - 1047   2017.7

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    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

  9. Rhenium-Catalyzed 1,1-Difunctionalization of 1,n-Diynes with Carbon Nucleophiles Followed by Sequential Cyclization Leading to Tetrahydroindenone Derivatives(共著)

    Masahito Murai, Erika Uemura, Shunsuke Hori, Kazuhiko Takai

    Angewandte Chemie International Edition   Vol. 56   page: 5862 - 5866   2017

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  10. Structural Characterization and Unique Catalytic Performance of Reactive Silyl-Substituted Geminal Dichromiomethane Complexes Stabilized with Diamine Ligand(共著)

    Masahito Murai, Ryuji Taniguchi, Naoki Hosokawa, Yusuke Nishida, Hiroko Mimachi, Toshiyuki Oshiki, Kazuhiko Takai

    Journal of American Chemical Society   Vol. 139   2017

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  11. Rhenium-Catalyzed ortho-Alkylation of Phenols(共著)

    Yoichiro Kuninobu, Masaki Yamamoto, Mitsumi Nishi, Tomoyuki Yamamoto, Takashi Matsuki, Masahito Murai, Kazuhiko Takai

    Organic Syntheses   Vol. 94   page: 280 - 291   2017

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Presentations 24

  1. 金属触媒を用いた炭化水素の効率的な機能化法の開発

    第13回触媒相模セミナー  2017 

  2. Selective Transposition of Double Bonds of Alkenes under Palladium Catalysis

    第65回 有機金属化学討論会  2018 

  3. Rhodium-catalyzed synthesis of sila[n]helicenes via dehydrogenative silylation of C-H bonds

    International Symposium on JST ACT-C Project  2017 

  4. Rhenium-Catalyzed Intermolecular anti-Markovnikov Addition Reaction of 1,3-Dicarbonyl Compounds with Terminal Alkynes

    28th International Conference on Organometallic Chemistry  2018 

  5. Rhenium-catalyzed construction of polycyclic hydrocarbon frameworks via the anti-Markovnikov addition of carbon nucleophiles

    International Symposium on JST ACT-C Project  2017 

  6. Rhenium-Catalyzed anti-Markovnikov Addition Reaction of Carbon Nucleophiles to Unactivated Terminal Acetylenes

    Rhenium-Catalyzed anti-Markovnikov Addition Reaction of Carbon Nucleophiles to Unactivated Terminal Acetylenes  2018 

  7. Rhenium-Catalyzed anti-Markovnikov Addition Reaction of Carbon Nucleophiles to Unactivated Terminal Acetylenes

    International Symposium on Pure & Applied Chemistry  2017 

  8. Regioselective Homologation of Arenes through Rhenium-Catalyzed Deoxygenative Aromatization of 7-Oxabicyclo[2.2.1]hepta-2,5-dienes

    第65回 有機金属化学討論会  2018 

  9. Regioselective benzoannulation of PAHs via the rhenium-catalyzed deoxygenation of 7-oxabicyclo[2.2.1]hepta-2,5-diene

    International Symposium on JST ACT-C Project  2017 

  10. Reactivity and Catalytic Performance of Geminal Dichromiomethane Complexes Stabilized with Diamine Ligands

    第64回 有機金属化学討論会  2017 

  11. Iridium-Catalyzed Sequential Silylation and Borylation of Heteroarenes Based on the Regioselective Two Different C-H Bond Activation

    4th International Symposium on C-H Activation  2018 

  12. Iridium-catalyzed sequential silylation and borylation of heteroarenes based on the regioselective C-H bond activation

    International Symposium on JST ACT-C Project  2017 

  13. Iridium-catalyzed hydrosilylation of cyclopropanes via regioselective carbon-carbon bonds cleavage

    第64回 有機金属化学討論会  2017 

  14. gem-二クロムシリルメタン錯体の構造解析と触媒反応への利用

    日本化学会第97春季年会  2017 

  15. レニウム触媒による2-アルケニルフェノールとアルキンの付加反応によるベンゾピラン誘導体の合成

    日本化学会第97春季年会  2017 

  16. レニウム触媒による7-オキサビシクロ[2.2.1]ヘプタ-2,5-ジエンの脱酸素反応を利用する位置選択的なπ共役系の拡張

    日本化学会第98春季年会  2018 

  17. レニウム触媒によるオレフィンの二重結合の選択的な移動反応

    日本化学会第97春季年会  2017 

  18. 位置選択的な炭素-水素結合の活性化によるヘテロ芳香環の連続的なケイ素化-ホウ素化反応

    日本化学会第97春季年会  2017 

  19. 塩化クロム(II)を用いるアルケンの立体選択的ボリルシクロプロパン化反応

    日本化学会第97春季年会  2017 

  20. 金属活性種の設計に基づく炭化水素の選択的な直截官能基化

    日本化学会第98春季年会  2018 

  21. 金属触媒による配向基を用いない不飽和炭化水素の官能基化

    京大人環 分子環境相関論サマーセミナー2018  2018 

  22. Transition Metal-Catalyzed Intermolecular Dehydrogenative Silylation of Aromatic Compounds without Directing Groups Based on the Regio- and Chemoselective C-H Bond Activation

    8th Annual Global Congress of Catalysis 2017  2017 

  23. ヘテロ配向基を用いない不飽和分子の位置選択的な直截官能基化

    第45回オルガノメタリックセミナー  2018 

  24. イリジウム触媒によるヘテロ芳香環のC-H結合の位置選択的ケイ素化-ホウ素化反応

    第111回有機合成シンポジウム2017年 春  2017 

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KAKENHI (Grants-in-Aid for Scientific Research) 4

  1. 5~7族の金属錯体の個性を活かした触媒的な高難度変換反応の開発

    Grant number:19H02719  2019.4 - 2023.3

    科学研究費補助金-基盤(B) 

    村井 征史

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    Authorship:Principal investigator 

    Grant amount:\15210000 ( Direct Cost: \11700000 、 Indirect Cost:\3510000 )

    5~7族の金属錯体は、様々な原子価や酸化状態を取れる性質から、これまで重合や酸化反応に使われることが多かった。本研究では、利用形式が限られているこれらの金属に焦点を当て直し、5~7族の金属錯体でなければ達成できない触媒的な高難度物質変換法の確立を目指す。具体的には、これらの金属錯体を「単体で用い、ユニークな脱酸素反応や求核的なアルキリデン錯体発生法」、「他の触媒と複合して用い、二重結合の移動や脱水素を伴う炭素-炭素結合形成反応」をそれぞれ開発できないか検討する。金属の個性の発見・開拓・応用により、実用的な合成反応の開発を目指す。
    2019年は5~7族元素の内、6族のクロムと7族のレニウムを用い、以下の三つの変換反応を論文として発表した。
    適切なジアミン配位子存在下、1,1-ジヨードメチルスズに塩化クロム(II)を作用させることで、一及び二置換オレフィンから、対応するスタニルシクロプロパン誘導体が収率良く得られることを見出した。いずれの基質との反応からも、オレフィンの置換基とスタニル基は立体障害を避け、トランスに位置した生成物のみが選択的に得られた。スタニル基(Sn)を、シリル基(Si)やゲルミル基(Ge)等の他の14族元素に変えたgem-ジクロムメタンと反応性を比較した結果、Sn>Si>Geの順番であることが分かった。導入したスタニル基は、立体配置を維持したまま、Stilleカップリングやスズ-リチウム交換により、他の官能基へと変換することができた。
    フェノールの内部アルキンへの付加反応がレニウム触媒により促進され、位置選択的にモノアルケニル化体が生成した後、ベンゾピラン誘導体へとさらに変換されることを見出した。フェノールの内部アルキンへの付加による触媒的な分子間アルケニル化反応は過去に報告がなく、初めての例であった。ベンゾピラン誘導体の形成は、フェノールとアルキン二分子による[3+2+1]環化付加反応と見なすことができ、カルボメタル化の形式が反応中に変化し、アルキンが二炭素ユニットと一炭素ユニットの両方として機能する珍しい反応であった。これらの新規反応は、フェノール性ヒドロキシ基が配向基として機能し、促進されていたと考えられる。レニウム活性種を単結晶X線解析により構造決定するとともに、その知見からレニウム触媒の活性を向上させることもできた。
    レニウム触媒による官能基化ヨードアルキンの1,2-ヨード及び1,5-ヒドリド転位を経る2-ヨードインデン誘導体の合成法も見出したが、文字数の都合上、詳細は割愛する。
    当初の計画通り、5~7族の金属触媒や反応剤を用いることで、他の金属では実現不可能な変換反応をいくつか見出した。前期と後期の中間に位置するクロムやレニウム錯体の新しい潜在性を引き出すことができたことから、研究はおおむね順調に進行していると言える。また、クロム塩を用いるエンインやアルキニルケトンの環化反応も見出し、予備的にではあるが反応の大枠を捉えることができた。次年度に、基質の適用範囲や特異な反応性が発現した要因を明らかにするための準備を整えることができた。
    1年目の後半に見出したgem-ジクロムメタンのエンインやアルキニルケトンに対する付加と環化反応の詳細を調べる。ケトカルボニル基との反応形式から、この反応ではgem-ジクロムメタン錯体からSchrock型の求核的なカルベン種が発生していることが示唆される。反応の適用範囲の調査に加え、活性種の単離及び構造解析を目指す。また、ケトカルボニル基以外の求電子剤での捕捉を通じ、新形式の環化反応を開発する。

  2. Development of new reactivity of novel metal-alkylidene and -carbene compllexes

    Grant number:18H03911  2018.4 - 2022.3

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    Authorship:Coinvestigator(s) 

  3. Development of unique pai-conjugated smart materials based on the catalytic and regioselective functionalization of azulenes

    Grant number:16K05778  2016.4 - 2020.3

    Murai Masahito

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    Authorship:Principal investigator 

    Grant amount:\4550000 ( Direct Cost: \3500000 、 Indirect Cost:\1050000 )

    Uniquely polarized hydrocarbon, azulene, possesses unusual photophysical and electrochemical properties that are unique for small molecules without any hetero atoms. The main purpose of the present study is development of a regioselective functionalization methods to further extend and disclose its potential new functions. As a result of investigation, (1) regioselective direct arylation of the carbon-hydrogen bond of azulene, (2) method for incorporation of azulene rings into phenacene and acene skeletons, and (3) regioselective arene homologation through deoxygenative aromatization were developed, and the performance of the resulting products as components for organic field-effect transistors was evaluated.

  4. Development of Innovative Synthetic Reactions Based on Diverse Reactivity of Group 6 and 7 Metals and their Complexes

    Grant number:26248030  2014.4 - 2018.3

    TAKAI KAZUHIKO

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    Authorship:Coinvestigator(s) 

    Through this research, we tried to clarify the features of the group 6-7 metals, especially unknown and useful reactivities for organic synthesis. We have found the following synthetic reactions by using the metal complexes. (1) Isolation of silyl-substituted gem-dichromiomethane (and gem-dizinciomethane) complexes and examination of the catalytic reactivity of the isolated complexes toward olefins and carbonyl compounds; (2) Intermolecular anti-Markovnivov addition of carbon nucleophiles by generation of rhenium-alkylidene complexes from terminal alkynes; (3) Molybdenum-catalyzed hydrosilylation of allenes and deoxygenation of epoxides; (4) Novel bismuth-catalyzed electrophilic C-C bond formation and etherification of phenolic hydroxy groups.

Industrial property rights 2

  1. ニトロ基を有する9-シラフルオレン化合物及びその製造方法

    村井征史, 高井和彦

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    Application no:特願2018-209329 

  2. 多環芳香族化合物及びその製造方法

    村井征史, 伊場真志, 高井和彦

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    Application no:特願2014-47900 

    Announcement no:Jpn. Kokai Tokkyo Koho (2015), JP 2015-172009 A 20151001 

 

Teaching Experience (On-campus) 1

  1. Current Organic & Polymer Chemistry

    2020

 

Social Contribution 1

  1. 県立岐阜北高校 系統別ガイダンス

    Role(s):Lecturer

    2020.10

Academic Activities 2

  1. 東海コンファレンス2021 in 愛知

    Role(s):Planning, management, etc., Panel moderator, session chair, etc.

    日本化学会東海支部  2021.12

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    Type:Competition, symposium, etc. 

  2. 第9回化学フロンティア研究会

    Role(s):Planning, management, etc., Panel moderator, session chair, etc.

    化学フロンティア研究会  2020.5

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    Type:Competition, symposium, etc.