Yamada, Toru

写真a

Affiliation

Faculty of Science and Technology, Department of Chemistry (Yagami)

Position

Professor

External Links

Career 【 Display / hide

  • 1987.04
    -
    1997.03

    三井石油化学工業株式会社

  • 1993.10
    -
    1994.03

    三井石油化学工業株式会社 室長研究員

  • 1994.04
    -
    1997.03

    三井石油化学工業株式会社 室長主任研究員

  • 1997.04
    -
    Present

    慶應義塾大学理工学部化学科 ,助教授

Academic Background 【 Display / hide

  • 1982.03

    The University of Tokyo, Faculty of Science, 化学科

    University, Graduated

  • 1984.03

    The University of Tokyo, Graduate School, Division of Science

    Graduate School, Completed, Master's course

  • 1987.03

    The University of Tokyo, Graduate School, Division of Science

    Graduate School, Completed, Doctoral course

Academic Degrees 【 Display / hide

  • 理学 , The University of Tokyo, 1987.03

 

Books 【 Display / hide

  • Silver Catalysis in Organic Synthesis

    Chao-Jun Li and Xihe Bi, Wiley-VCH, 2019.02

    Scope: Silver-Catalyzed CO2 Incorporation,  Contact page: 407-438

  • 7 Silver-Catalyzed CO2 Incorporation

    Yamada T., Sekine K., Sadamitsu Y., Saito K., Silver Catalysis in Organic Synthesis, 2018.12

  • 二酸化炭素を用いた化学品製造技術

    YAMADA TOHRU, S&T出版, 2016

    Scope: 87-105

  • 第5版実験化学講座17 日本化学会編

    YAMADA TOHRU, 2004

  • プロフェッショナル英和辞書SPED TERRA 物質・工学編

    YAMADA TOHRU, 2004

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Papers 【 Display / hide

  • Lewis Acid-catalyzed Decarboxylative Cyanation of Cyclic Enol Carbonates ®Access to Multi-substituted ¢-Ketonitriles®

    Yokoyama H., Dokai Y., Kimaru N., Saito K., Yamada T.

    Chemistry Letters (Chemistry Letters)  51 ( 4 ) 469 - 472 2022.04

    Joint Work,  ISSN  03667022

     View Summary

    A Lewis acid-catalyzed decarboxylative substitution reaction of cyclic enol carbonates with a cyanation reagent was developed to give ¢-ketonitriles in good yield. It is proposed that the reaction proceeds through an oxyallyl cation intermediate or its equivalent. Interestingly, cyanation selectively took place at the more hindered site of the intermediate to afford a multi-substituted ¢-ketonitrile. This regioselectivity was observed by the cyanation of a wide range of substrates and is discussed in terms of the reaction mechanism.

  • Microwave-specific enhancement of nazarov cyclization

    Kubota Y., Kawanori T., Sawada T., Saito K., Yamada T.

    Chemistry Letters (Chemistry Letters)  50 ( 1 ) 144 - 146 2021.01

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  03667022

     View Summary

    A copper-catalyzed Nazarov cyclization was carried out under conventional heating conditions and microwave conditions. Under strictly temperature-controlled conditions, the use of microwave irradiation improved the chemical yields. Consequently, the kinetic rate of the microwave irradiation was 5.8 times higher than that of the conventional heating conditions. These observations suggested that the microwave specific effects enhanced the efficiency of the Nazarov reaction.

  • Stereoselective amination: Via vinyl-silver intermediates derived from silver-catalyzed carboxylative cyclization of propargylamine

    Sadamitsu Y., Saito K., Yamada T.

    Chemical Communications (Chemical Communications)  56 ( 66 ) 9517 - 9520 2020.08

    ISSN  13597345

     View Summary

    © The Royal Society of Chemistry. The stereoselective synthesis of aminovinyloxazolidinones based on the electrophilic amination of a vinyl-silver intermediate, generated by silver-catalyzed carbon dioxide incorporation on a propargyl amine, was achieved. The geometry of the aminated product was determined by a single crystal X-ray analysis and NOE measurement and it was elucidated that the geometry was proved to be opposite to the geometry predicted from the previous silver-catalyzed carbon dioxide fixation on a propargyl amine derivative. This unexpected stereoselectivity could be successfully explained by a radical mechanism. This journal is

  • Thermal decarboxylative Nazarov cyclization of cyclic enol carbonates involving chirality transfer

    Kozuma A., Komatsuki K., Saito K., Yamada T.

    Chemistry Letters (Chemistry Letters)  49 ( 1 ) 60 - 63 2020

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  03667022

     View Summary

    © 2020 The Chemical Society of Japan. Decarboxylative Nazarov cyclization of chiral cyclic enol carbonates proceeded to afford chiral 2-cyclopentenones with excellent chirality transfer under thermal conditions without any catalyst. Interestingly, the thermal decarboxylative Nazarov cyclization furnished the desired product with better chirality transfer than the Lewis acid-catalyzed reaction.

  • Silver-Catalyzed Carbon Dioxide Fixation on Alkynylindenes

    Okumura A., Chuang P.Y., Saito K., Yamada T.

    Organic Letters (Organic Letters)   2020

    ISSN  15237060

     View Summary

    © The synthesis of polycyclic indene derivatives via silver-catalyzed carbon dioxide fixation on 2-alkynylindene derivatives was achieved by nucleophilic addition of the indenyl anion to carbon dioxide involving carbon-carbon bond formation and subsequent intramolecular cyclization to the alkyne part activated by a silver catalyst. This cascade process could be applied to various substrates to obtain the corresponding products in high yields. The endo/exo selectivity of the cyclization could be controlled by the steric or electronic effect of the substituents on the substrates, and 6-endo-selective cyclization was realized to afford α-pyrone-fused indenes.

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Papers, etc., Registered in KOARA 【 Display / hide

Reviews, Commentaries, etc. 【 Display / hide

  • Lewis Acid‐Mediated Decarboxylative Allylation of Enol Carbonates

    Yoichi Dokai and Takuma Nishizawa and Kodai Saito and Tohru Yamada

    Helvetica Chimica Acta (Wiley)  104 ( 7 )  2021.07

    Rapid communication, short report, research note, etc. (scientific journal), Joint Work,  ISSN  0018019X

     View Summary

    A homoallylic ketone can be transformed and functionalized by various synthetic reactions, and thus, is regarded as one of the representative building blocks in organic chemistry. An additional route to access homoallylic ketones, namely, a Lewis acid-mediated decarboxylative allylation of cyclic enol carbonates, prepared by fixation of carbon dioxide onto propargyl alcohols, was developed in this work. The treatment of a cyclic enol carbonate with a Lewis acid in the presence of an allylsilane resulted in the formation of a homoallylic ketone. It was found that the title reaction proceeded well by the combined use of zirconium tetrachloride with allyltrimethylsilane. The allylation occurred with high regioselectivity and the corresponding homoallylic ketones were obtained in good-to-high yields. A reaction mechanism involving the decarboxylative formation of an oxyallyl cation equivalent is proposed.

  • Decarboxylation-triggered homo-Nazarov cyclization of cyclic enol carbonates catalyzed by rhenium complex

    Natsuki Kimaru and Keiichi Komatsuki and Kodai Saito and Tohru Yamada

    Chemical Communications (Royal Society of Chemistry ({RSC}))  57 ( 50 ) 6133 - 6136 2021

    Rapid communication, short report, research note, etc. (scientific journal),  ISSN  13597345

     View Summary

    Decarboxylative homo-Nazarov cyclization catalyzed by a Lewis acid was achieved using a cyclic enol carbonate bearing a cyclopropane moiety as a substrate. Various substrates were converted into the corresponding multi-substituted cyclohexenones in good yieldsviadecarboxylation, followed by 6-membered ring formation involving cyclopropane-ring-opening.

  • Silver-Catalyzed Carbon Dioxide Fixation on Alkynylindenes

    Akira Okumura and Po-Yao Chuang and Kodai Saito and Tohru Yamada

    Organic Letters (American Chemical Society ({ACS}))  22 ( 21 ) 8648 - 8651 2020.11

    Rapid communication, short report, research note, etc. (scientific journal), Joint Work,  ISSN  15237060

     View Summary

    The synthesis of polycyclic indene derivatives via silver-catalyzed carbon dioxide fixation on 2-alkynylindene derivatives was achieved by nucleophilic addition of the indenyl anion to carbon dioxide involving carbon-carbon bond formation and subsequent intramolecular cyclization to the alkyne part activated by a silver catalyst. This cascade process could be applied to various substrates to obtain the corresponding products in high yields. The endo/exo selectivity of the cyclization could be controlled by the steric or electronic effect of the substituents on the substrates, and 6-endo-selective cyclization was realized to afford α-pyrone-fused indenes.

  • Stereoselective amination via vinyl-silver intermediates derived from silver-catalyzed carboxylative cyclization of propargylamine

    Yuta Sadamitsu and Kodai Saito and Tohru Yamada

    Chemical Communications (Royal Society of Chemistry ({RSC}))  56 ( 66 ) 9517 - 9520 2020

    Rapid communication, short report, research note, etc. (scientific journal),  ISSN  13597345

     View Summary

    The stereoselective synthesis of aminovinyloxazolidinones based on the electrophilic amination of a vinyl-silver intermediate, generated by silver-catalyzed carbon dioxide incorporation on a propargyl amine, was achieved. The geometry of the aminated product was determined by a single crystal X-ray analysis and NOE measurement and it was elucidated that the geometry was proved to be opposite to the geometry predicted from the previous silver-catalyzed carbon dioxide fixation on a propargyl amine derivative. This unexpected stereoselectivity could be successfully explained by a radical mechanism. This journal is

  • Decarboxylative Nazarov Cyclization-Based Chirality Transfer for Asymmetric Synthesis of 2-Cyclopentenones

    Keiichi Komatsuki and Akane Kozuma and Kodai Saito and Tohru Yamada

    Organic Letters (American Chemical Society ({ACS}))  21 ( 17 ) 6628 - 6632 2019.09

    Rapid communication, short report, research note, etc. (scientific journal),  ISSN  15237060

     View Summary

    Asymmetric synthesis of 2-cyclopentenones was achieved by chirality transfer based on Lewis acid catalyzed decarboxylative Nazarov cyclization of optically active cyclic enol carbonates, which are prepared by silver-catalyzed carbon dioxide incorporation into optically pure propargyl alcohols. The stereochemistry at the 4,5-positions of the 2-cyclopentenones was cleanly constructed by reflecting the stereochemistry of the starting materials. This method could be applied to various substrates to obtain the corresponding products in high yields with highly efficient chirality transfer.

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Presentations 【 Display / hide

  • 脱炭酸型ナザロフ環化反応による2-シクロペンテノン誘導体の合成

    上妻紅音,駒月恵一,齊藤巧泰,山田 徹

    日本化学会第99春季年会, 

    2019.03

    Oral presentation (general)

  • 銀触媒を用いるアルキニルインデン誘導体に対する二酸化炭素固定化反応

    奥村晶,荘 博尭,齊藤巧泰,山田 徹

    日本化学会第99春季年会, 

    2019.03

    Oral presentation (general)

  • マイクロ波の加熱効果と特異効果:有機合成反応への適用

    山田 徹

    日本化学会第99春季年会, 

    2019.03

    Oral presentation (invited, special)

  • Silver-Catalyzed Carbon-Carbon Bond Formation with Carbon Dioxide

    T. Yamada

    China-Japan Joint Symposium on Catalysis for Transformation of Carbon Dioxide, 

    2019.01

    Oral presentation (invited, special)

  • Microwave Specific Effect on Catalytic Enantioselective Reaction

    Tohru Yamada

    International Symposium on Catalysis and Fine Chemicals, 

    2018.12

    Oral presentation (invited, special)

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Research Projects of Competitive Funds, etc. 【 Display / hide

  • Study on the Mechanism and the General Application of Microwave Specific Effects on Synthetic Organic Chemistry

    2021.04
    -
    2024.03

    Keio University, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (C), No Setting

     View Summary

    有機合成反応に対するマイクロ波作用は,熱的効果に加えマイクロ波特異効果の存在が議論されてきた。申請者は触媒的不斉合成反応へのマイクロ波適用により,それらの分離に成功した。本研究ではマイクロ波特異効果の適用一般化を目指し,マイクロ波照射で加速される反応系の開拓と,定量的取り扱い,反応速度論解析により,有機合成化学におけるマイクロ波適用の指針を示し,有機合成反応開発の革新発展に寄与することを目指す。

  • Synthetic Organic Chemistry with a New Concept of Microwave Chemistry

    2017.04
    -
    2020.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, YAMADA TOHRU, Grant-in-Aid for Scientific Research (B), Principal investigator

     View Summary

    The microwave specific effect was verified in the Nazarov cyclization reaction. Based on the quantification of the reaction acceleration by kinetic analysis, the maximum acceleration of 5.8 times was confirmed. Reaction acceleration was also observed in the thermal Nazarov cyclization reaction without any loss of chiral transfer rate. In the development research of absolute asymmetric synthesis using circularly polarized microwaves, a joint research was made on the setting of reaction system by physical measurement of circularly polarized microwaves. Furthermore, we have developed a joint research on the hypothesis that the microwave specificity effect is based on entropy effect, and found a possibility to elucidate the mechanism by terahertz spectroscopy.

  • Synthetic Study on Chirality Control with Circular Polarized Microwave

    2015.04
    -
    2017.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, Grant-in-Aid for Challenging Exploratory Research, Principal investigator

     View Summary

    The effect of circularly polarized microwave irradiation was examined. Substrate was charged, without irradiation, or under right-handed / left-handed CPM irradiation, and the ee of the reduced product was analyzed. When the asymmetric catalysis was irradiated with 12.4 GHz CPM, the ee under the right-handed conditions was improved more than the non-irradiated conditions, but decreased in the left-handed conditions. In the 2.45 GHz / 50 W CPM irradiation to the racemic catalytic reaction, both the right-handed and the left-handed conditions improved, and the microwave effect should be considered.
    The CPM effect on atropo-isomerization reaction was examined. After 2.45 GHz / 20 W CPM irradiation, the ee was analyzed after reduction to prevent from racemization. As a result of the statistical processing, we found reaction conditions that the enantiomeric excess was observed in the opposite directions on the left-handed and the right-handed, though in the racemic 95% confidence interval.

Intellectual Property Rights, etc. 【 Display / hide

  • 光学活性イソオキサゾリン類の製造方法

    Date applied: 特願2002-64038  2002.03 

    Patent

  • エポキシ基含有化合物の製造方法

    Date applied: 特願2001-046082  2001.02 

    Patent

  • 光学活性コバルト(II)、及びコバルト(III)錯体、その中間体の製造方法

    Date applied: 特願2000-344191  2000.11 

    Patent

  • 光学活性1,3-プロパンジオール類の製造方法

    Date applied: 特願2000-70712  2000.03 

    Patent

  • 光学活性シクロプロパン誘導体の製造方法

    Date applied: 特願平11-163426  1999.06 

    Patent

Awards 【 Display / hide

  • SSOCJ Nissan Chemical Industries Award for Novel Reaction & Method 2009

    YAMADA TOHRU, 2010.02, Development of Optically Active Cobalt Complex Catalysts for Enantioselective Synthetic Reactions

    Type of Award: Award from Japanese society, conference, symposium, etc.

  • 平成4年度日本化学会進歩賞

    山田 徹, 1993.03, 日本化学会

 

Courses Taught 【 Display / hide

  • TOPICS IN STEREOSELECTIVE ORGANIC REACTIONS

    2022

  • SYNTHETIC ORGANIC REACTIONS (BASIC ORGANIC CHEMISTRY 2)

    2022

  • SEMINAR IN CHEMISTRY

    2022

  • SELECTIVE ORGANIC REACTIONS (ORGANIC CHEMISTRY 2)

    2022

  • ORGANIC STRUCTURE AND REACTIONS (BASIC ORGANIC CHEMISTRY 1)

    2022

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Memberships in Academic Societies 【 Display / hide

  • 日本化学会, 

    1981
    -
    Present
  • 有機合成化学協会, 

    1994
    -
    Present
  • 日本薬学会, 

    1996
    -
    Present
  • 近畿化学協会, 

    2005
    -
    Present
  • 日本電磁波エネルギー応用学会, 

    2018
    -
    Present

Committee Experiences 【 Display / hide

  • 2005.04
    -
    2006.03

    代議員, 近畿化学協会

  • 2004.11
    -
    2005.10

    関東支部平成17年度代議員, 日本化学会

  • 2004.04
    -
    2006.02

    関東支部常任幹事, 日本化学会

  • 2004.02
    -
    2006.02

    関東支部常任幹事, 有機合成化学協会

  • 2003.11
    -
    2004.10

    関東支部平成16年度代議員, 日本化学会

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