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New Generation in Deuterium Chemistry: Development of Novel Deuterated Organocatalysts and Biologically Interesting Molecules

Research Project

Project/Area Number 15K13644
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Organic chemistry
Research InstitutionKochi University

Principal Investigator

Kotsuki Hiyoshizo  高知大学, 学内共同利用施設等, 特任教授 (80093954)

Co-Investigator(Renkei-kenkyūsha) ICHIKAWA Yoshiyasu  高知大学, 教育研究部自然科学系, 教授 (60193439)
NAKANO Keiji  高知大学, 教育研究部自然科学系, 准教授 (50399747)
Project Period (FY) 2015-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords有機分子触媒 / 重水素化有機触媒 / 生体機能性分子 / チオ尿素触媒 / 重水素化 / 有機不斉触媒 / 有機アミン系触媒 / カルボニル/エン環化反応 / 生物活性天然物 / マイクロウェーヴ反応 / 不斉Michael付加反応 / 生物活性天然物合成
Outline of Final Research Achievements

The purpose of this project has been focused on the development of a new selective method for deuteration of organocatalysts and biologically interesting molecules. As a result, we could succeed in synthesizing new deuterated thiourea organocatalysts for the use in novel synthetic reactions. For example, we found that a catalytic system composed of trityl halide and thiourea catalyst could serve as novel organo-based Lewis acids for the use in carbonyl-ene cyclization. In addition, we also found that the asymmetric Michael addition reaction of alpha-substituted cyclic ketones was efficiently promoted by primary amine-based organocatalysts under high pressure conditions. Finally, we could also succeed in obtaining a new approach to introduce deuterium atoms into the biologically interesting molecules. We believe that these results will give important information for other chemists who work in this important field.

Report

(3 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • Research Products

    (34 results)

All 2017 2016 2015 Other

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Acknowledgement Compliant: 9 results,  Open Access: 1 results) Presentation (19 results) (of which Int'l Joint Research: 3 results,  Invited: 6 results) Book (1 results) Remarks (2 results)

  • [Journal Article] Trityl cation catalyzed intramolecular carbonyl-ene cyclization and [2+2] cycloaddition2017

    • Author(s)
      Nomoto, Y.; Horinouchi, R.; Nishiyama, N.; Nakano, K.; Ichikawa, Y.; KOTSUKI, H.
    • Journal Title

      Synlett

      Volume: 28 Issue: 02 Pages: 265-269

    • DOI

      10.1055/s-0036-1588618

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Heteropoly acid supported on silica gel catalyzed the asymmetric transfer allylation of aromatic aldehydes under solvent-free conditions2017

    • Author(s)
      Nunokawa, S.; Oki, K.; Yamashita, K.; Okuyama, A.; Ueda, T.; Nakano, K.; Ichikawa, Y.; KOTSUKI, H.
    • Journal Title

      Synlett

      Volume: 28 Issue: 05 Pages: 597-600

    • DOI

      10.1055/s-0036-1588121

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A direct method for beta-selective glycosylation with an N-acetylglucosamine donor armed by a TBDMS protecting group2017

    • Author(s)
      Tanaka, H.; Hamaya, Y.; KOTSUKI, H.
    • Journal Title

      Molecules

      Volume: 22 Issue: 3 Pages: 429-437

    • DOI

      10.3390/molecules22030429

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of trans-2,6-piperidinedicarboxamide using the Ugi reaction. A plausible model for the biosynthesis of halichonadin P2016

    • Author(s)
      Mimura, R.; Kitamori, A.; Nakano, K.; KOTSUKI, H.; Matsumoto, K.; Kaneno, D.; Masuda, T.; Ichikawa, Y.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 5 Pages: 857-865

    • DOI

      10.3987/com-16-13422

    • NAID

      40020825865

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A biomimetic approach to the synthesis of terpene-amino acid conjugates. The Ugi reaction in the hypothetical biosynthesis of marine natural products2016

    • Author(s)
      Ichikawa, Y.; Saito, K.; Mimura, R.; Kitamori, A.; Matsukawa, A.; Ikeda, A.; Masuda, T.; KOTSUKI, H.; Nakano, K.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 6 Pages: 1040-1053

    • DOI

      10.3987/com-16-13442

    • NAID

      40020862298

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] An organocatalytic asymmetric Diels-Alder strategy for the enantioselective synthesis of spirocyclic oxindole- cyclohexenones2016

    • Author(s)
      Matsugi, A.; Nunokawa, S.; Watanabe, N.; Nakata, Y.; Nakano, K.; Ichikawa, Y.; KOTSUKI, H.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 11 Pages: 1953-1961

    • DOI

      10.3987/com-16-13562

    • NAID

      40021014906

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of beta-glycosyl formamides through N-glycosylation of unprotected carbohydrates2016

    • Author(s)
      Ichikawa, Y.; Matsukawa, A.; Maeda, M.; Tomita,Y.; Mimura, R.; Kitamori, A.; KOTSUKI, H.; Nakano, K.; Masuda, T.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 12 Pages: 2201-2212

    • DOI

      10.3987/com-16-13584

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A NEW STRATEGY FOR SYNTHESIS OF THE DINUCLEOTIDE pdCpA: A CONVENIENT METHOD FOR THE DEPROTECTION OF CYANOETHYL, TBDMS, AND BENZOYL GROUPS IN ONE STEP AT HIGH PRESSURE2015

    • Author(s)
      2.Masanori Kataoka, Chiharu Fukui, Akiko Mimoto, Hideaki Kuge, Koichi Honke, and Hiyoshizo Kotsuki
    • Journal Title

      HETEROCYCLES

      Volume: 91 Issue: 6 Pages: 1164-1169

    • DOI

      10.3987/com-15-13223

    • NAID

      40020504668

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Quaternary Carbon Stereogenic Centers through the Primary Amine-catalyzed Michael Addition Reaction of α-Substituted Cyclic Ketones at High Pressure2015

    • Author(s)
      Horinouchi, R.; Kamei, K.; Watanabe, R.; Hieda, N.; Tatsumi, N.; Nakano, K.; Ichikawa, Y.; KOTSUKI, H.
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2015 Issue: 20 Pages: 4457-4463

    • DOI

      10.1002/ejoc.201500411

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Biomimetic Approaches Employing the Ugi Five-Center Four-Component Reaction for Synthesis of the Right-Hand Portion of Halichonadin Q and the Central Part of Halichonadin M2015

    • Author(s)
      Mimura, R.; Kitamori, A.; Ikeda, A.; Matsuda, T.; Nakano, K.; KOTSUKI, H.; Ichikawa, Y.
    • Journal Title

      Synthesis

      Volume: 47 Issue: 19 Pages: 3043-3048

    • DOI

      10.1055/s-0034-1380438

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Asymmetric Michael Addition Reaction of α-Aryl-substituted Lactams Catalyzed by Chiral Quaternary Ammonium Salts Derived from Cinchona Alkaloids: A New Short Synthesis of (+)-Mesembrine2015

    • Author(s)
      Nunokawa, S.; Minamisawa, M.; Nakano, K.; Ichikawa, Y.; KOTSUKI, H.
    • Journal Title

      Synlett

      Volume: 26 Issue: 16 Pages: 2301-2305

    • DOI

      10.1055/s-0035-1560090

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] 有機不斉触媒反応を活用した第四級不斉炭素中心含有生物活性天然物の合成2015

    • Author(s)
      小槻日吉三
    • Journal Title

      文部科学省科研費・新学術領域研究「有機分子触媒による未来型分子変換」,平成25年度研究成果報告書

      Volume: 2015 Pages: 231-234

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] ヘテロポリ酸担持シリカゲル触媒活用不斉アリル転写2017

    • Author(s)
      布川しおり,沖和也,山下恵祐,奥山敦史,上田忠治,小槻日吉三
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 有機不斉触媒活用不斉識別反応:(-)-Lycoramineの不斉全合成への応用2017

    • Author(s)
      布川しおり,川北安理紗,小槻日吉三
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] トリチルカチオン有機触媒反応:高圧条件下でのイミノ―エン環化反応2017

    • Author(s)
      村上弘樹,小槻日吉三
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 有機不斉触媒反応活用不斉Diels-Alder反応を用いたスピロ置換型オキシインドール類のエナンチオ選択的合成2016

    • Author(s)
      布川しおり,渡部忠尚,中田裕也,小槻日吉三
    • Organizer
      第9回有機触媒シンポジウム
    • Place of Presentation
      名古屋大学
    • Year and Date
      2016-12-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] 天然物合成の魅力:もの作りはひと作り2016

    • Author(s)
      小槻日吉三
    • Organizer
      伏見製薬化学講演会
    • Place of Presentation
      丸亀市
    • Year and Date
      2016-11-29
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] GlcNAc- Asn担持ジヌクレオチドの効率的合成2016

    • Author(s)
      片岡正典,福井千春,小槻日吉三,本家孝一
    • Organizer
      第35回日本糖質学会年会
    • Place of Presentation
      高知市
    • Year and Date
      2016-09-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] 有機化学のすゝめ―No Challenge, No Chemistry!2016

    • Author(s)
      小槻日吉三
    • Organizer
      グリーンサイエンス講演会
    • Place of Presentation
      高知大学
    • Year and Date
      2016-07-15
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 生物活性天然物の不斉合成研究2016

    • Author(s)
      小槻日吉三
    • Organizer
      第46回アカデミアセミナー(バイオマス講演会)
    • Place of Presentation
      高知大学
    • Year and Date
      2016-06-21
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 天然物合成化学の魅力:高知大学からの発信2016

    • Author(s)
      小槻日吉三
    • Organizer
      広島大学工学部化学講演会
    • Place of Presentation
      広島大学
    • Year and Date
      2016-05-13
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] ハロゲン化トリチル/チオ尿素:トリチルカチオンによる触媒的分子内カルボニル―エン環化反応及び[2+2]環化付加反応2016

    • Author(s)
      堀之内僚, 野本裕也,西山伸雄, 小槻日吉三
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      京都府京田辺市
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] 有機不斉触媒反応を活用した第四級不斉炭素中心含有生物活性天然物の合成2016

    • Author(s)
      小槻日吉三
    • Organizer
      有機分子触媒による未来型分子変換 第6回公開シンポジウム
    • Place of Presentation
      大阪府大阪市
    • Year and Date
      2016-01-22
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] Thiourea-Catalyzed Generation of Trityl Cation Species: Application to Carbonyl-Ene Cyclization Reaction2015

    • Author(s)
      N. Nishiyama, R. Horinouchi, H. Kotsuki
    • Organizer
      2015 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2015)
    • Place of Presentation
      Hawaii, Honolulu
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Efficient Enantioselective Synthesis of All-Carbon- Substituted Quaternary Carbon Stereogenic Centers through the Pripary Amine-Based Organocatalytic Michael Addition Reaction of α-Substituted Cyclic Ketones at High Pressure2015

    • Author(s)
      R. Horinouchi, K. Kamei, R. Watanabe, N. Hieda, N. Tatsumi, H. Kotsuki
    • Organizer
      2015 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2015)
    • Place of Presentation
      Hawaii, Honolulu
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Asymmetric Organocatalytic Michael Addition Reaction of α-Aryl-substituted Lactams by Phase Transfer Catalyst: A New Short Synthesis of (+)-Mesembrine2015

    • Author(s)
      S. Nunokawa, M. Minamisawa, H. Kotsuki
    • Organizer
      2015 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2015)
    • Place of Presentation
      Hawaii, Honolulu
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] 第四級キラルアンモニウム塩を触媒とするα-アリール置換ラクタム類の不斉Michael付加反応:(+)-Mesembrineの不斉全合成への適用2015

    • Author(s)
      布川しおり, 南澤将光, 小槻日吉三
    • Organizer
      第3回高知大学―高知工科大学ジョイントシンポジウム
    • Place of Presentation
      高知県高知市
    • Year and Date
      2015-11-28
    • Related Report
      2015 Research-status Report
  • [Presentation] 第四級キラルアンモニウム塩を触媒とするα-アリール置換ラクタム類の不斉Michael付加反応:(+)-Mesembrineの不斉全合成への適用2015

    • Author(s)
      布川しおり, 南澤将光, 小槻日吉三
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      東京都早稲田
    • Year and Date
      2015-11-19
    • Related Report
      2015 Research-status Report
  • [Presentation] チオ尿素系有機触媒を活用したトリチルカチオン種の発生:カルボニル―エン環化反応への適用2015

    • Author(s)
      堀之内僚, 野本裕也, 西山伸雄, 小槻日吉三
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      東京都早稲田
    • Year and Date
      2015-11-19
    • Related Report
      2015 Research-status Report
  • [Presentation] 大学で研究するということ―感動との出逢いを求めて2015

    • Author(s)
      小槻日吉三
    • Organizer
      高大連携化学系フォーラム2015
    • Place of Presentation
      高知県高知市
    • Year and Date
      2015-11-08
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] チオ尿素系有機触媒を活用したトリチルカチオン種の発生:カルボニル―エン環化反応への適用2015

    • Author(s)
      堀之内僚, 野本裕也,西山伸雄,小槻日吉三
    • Organizer
      第31回若手化学者のための化学道場
    • Place of Presentation
      兵庫県淡路
    • Year and Date
      2015-08-27
    • Related Report
      2015 Research-status Report
  • [Book] 化学研究最前線―土佐で夢追う研究者たち: キラリと光るキラルなものの作り方―不斉合成化学の魅力2015

    • Author(s)
      小槻日吉三
    • Total Pages
      10
    • Publisher
      飛鳥出版室
    • Related Report
      2015 Research-status Report
  • [Remarks] 高知大学理学部天然物化学研究室

    • URL

      http://www.cc.kochi-u.ac.jp/~kotsuki/

    • Related Report
      2016 Annual Research Report
  • [Remarks] 高知大学理学部天然物化学研究室

    • URL

      http://www.c.kochi-u.ac.jp/~kotsuki/

    • Related Report
      2015 Research-status Report

URL: 

Published: 2015-04-16   Modified: 2018-03-22  

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