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Development of Molecular Transforming System Using Organocatalytic Aromatic Deprotonation

Planned Research

Project AreaAdvanced Molecular Transformations by Organocatalysts
Project/Area Number 23105009
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionTohoku University

Principal Investigator

Kondo Yoshinori  東北大学, 薬学研究科(研究院), 教授 (90162122)

Research Collaborator TANAKA Yoshiyuki  徳島文理大学, 薬学部, 教授
INAMOTO Kiyofumi  武庫川女子大学, 薬学部, 准教授
KUMADA Kanako  東北大学, 大学院薬学研究科, 助手
Project Period (FY) 2011-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥51,870,000 (Direct Cost: ¥39,900,000、Indirect Cost: ¥11,970,000)
Fiscal Year 2015: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000)
Fiscal Year 2014: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000)
Fiscal Year 2013: ¥11,700,000 (Direct Cost: ¥9,000,000、Indirect Cost: ¥2,700,000)
Fiscal Year 2012: ¥11,570,000 (Direct Cost: ¥8,900,000、Indirect Cost: ¥2,670,000)
Fiscal Year 2011: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Keywords有機分子触媒 / 脱プロトン化 / 芳香環 / 芳香族複素環 / アミド塩基 / C-H修飾反応 / メタルフリー / 有機触媒 / ホスファゼン / 結合活性化 / HMDSアミド塩基 / ケイ素化 / 官能基 / 選択性 / 分子変換 / 芳香複素環 / オニウムアミド / 炭素アニオン / 有機ケイ素 / 二酸化炭素 / 脱プロトン / ヘテロ環 / 複素環
Outline of Final Research Achievements

Arenes and heteroarenes have been widely used in the structure of various drug candidates. The development of new methodology for the C-H functionalization of aromatic molecules is considered to be one of the most important subjects in medicinal oriented organic synthesis. Many kind of transition metalcatalyzed reactions have been employed for the selective modification of aromatic molecules, but the comtamination of heavy metals in the precursors of drug syntheses is strictly regulated. In this project, develpment of organocatalytic systems for selective C-H functionalization of aromatic molecules was investigated without using transition metal catalyzed processes. Especially, new deprotonative functionalizations were achieved by using in situ generated amide base catalyst.

Report

(6 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • Research Products

    (45 results)

All 2016 2015 2014 2013 2012 2011 Other

All Journal Article (16 results) (of which Peer Reviewed: 16 results,  Acknowledgement Compliant: 6 results) Presentation (25 results) (of which Int'l Joint Research: 1 results) Remarks (4 results)

  • [Journal Article] Development of Madelung-Type Indole Synthesis Using Copper-Catalyzed Amidation/Condensation Strategy2016

    • Author(s)
      Abe, Masahiro; Denneval, Charline; Nozawa-Kumada, Kanako; Kondo, Yoshinori
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 5 Pages: 900-900

    • DOI

      10.3987/com-16-13440

    • NAID

      40020825921

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Catalyzed sp3 C-H Aminative Cyclization of 2-Alkyl-N-arylbenzamides: An Approach for the Synthesis of N-Arylisoindolinones2015

    • Author(s)
      Nozawa-Kumada, Kanako; Kadokawa, Jun; Kameyama, Takahiro; Kondo, Yoshinori
    • Journal Title

      Organic Letters

      Volume: 17 Issue: 18 Pages: 4479-4481

    • DOI

      10.1021/acs.orglett.5b02235

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Deprotonative C-H solylation of functionalizaed arenes and heteroarenes using trimethyl -trialkylsilane with fluoride2015

    • Author(s)
      Sasaki, Midori; Kondo, Yoshinori
    • Journal Title

      Org. Lett.

      Volume: 17 Issue: 4 Pages: 848-851

    • DOI

      10.1021/ol503671b

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Use of tetramehylammonium fluoride (TMAF) and alkali metal alkoxides as an activator for catalytic deprotonative functionalization of heteroaromatic C(sp2)-H2014

    • Author(s)
      Inamoto, Kiyofumi; Okawa, Hitomi; Kikkawa, Shoko; Kondo, Yoshinori,
    • Journal Title

      Tetrahedron

      Volume: 70 Issue: 43 Pages: 7917-7922

    • DOI

      10.1016/j.tet.2014.08.054

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Direct condensation of functionalized sp3 carbons with formamides for enamine synthesis using an in situ generated HMDS amide catalyst2014

    • Author(s)
      Taneda, Hiroshi; Inamoto, Kiyofumi; Kondo, Yoshinori
    • Journal Title

      Chem. Commun.

      Volume: 50 Issue: 49 Pages: 6523-6525

    • DOI

      10.1039/c4cc02228a

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Desilylative carboxylation of aryltrimethylsilanes using CO2 in the presence of catalytic phosphazenium salt2014

    • Author(s)
      Yonemoto-Kobayashi, Misato; Inamoto, Kiyofumi, Kondo, Yoshinori
    • Journal Title

      Chem. Lett.

      Volume: 43 Issue: 4 Pages: 477-479

    • DOI

      10.1246/cl.131108

    • NAID

      130004868067

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Facile deprotection of dithioacetals by using a novel 1,4-benzoquinone/cat. NaI system2013

    • Author(s)
      Kiyofumi Inamoto, Tetsuya Yamada, Sei-ichi Kato, Shoko Kikkawa, Yoshinori Kondo
    • Journal Title

      Tetrahedron

      Volume: 69 Issue: 44 Pages: 9192-9199

    • DOI

      10.1016/j.tet.2013.08.061

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed Carbonylative C-H Cyclization of 2-Arylphenols: A Novel Synthetic Route to 6H-Dibenzo[b,d]pyran-6-one2013

    • Author(s)
      Kiyofumi Inamoto, Jun Kadokawa, Yoshinori Kondo
    • Journal Title

      Organic Letters

      Volume: 15 Issue: 15 Pages: 3962-3965

    • DOI

      10.1021/ol401734m

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organocatalytic functionalization of heteroaromatic N-oxides with C-nucleophiles using in situ generated onium amide bases2013

    • Author(s)
      Kiyofumi Inamoto, Yuta Araki, Shoko Kikkawa, Misato Yonemoto, Yoshiyuki Tanaka, Yoshinori Kondo
    • Journal Title

      Organic &Biomolecular Chemistry

      Volume: 11 Issue: 27 Pages: 4438-4441

    • DOI

      10.1039/c3ob40782a

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organocatalytic deprotonative functionalization of C(sp2)-H and C(sp3)-H bonds using in situ generated onium amide2012

    • Author(s)
      K. Inamoto, H. Okawa, H. Taneda, M. Sato, Y. Hirono, M. Yonemoto, Y. Kondo
    • Journal Title

      Chemical Communications

      Volume: 48 Issue: 78 Pages: 9771-9773

    • DOI

      10.1039/c2cc35701a

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed C-H cyclization in water: a milder route to2-arylbenzothiazoles2012

    • Author(s)
      Kiyofumi Inamoto, Kanako Nozawa, Yoshinori Kondo
    • Journal Title

      Synlett

      Volume: 23 Issue: 11 Pages: 1678-1682

    • DOI

      10.1055/s-0031-1291164

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient useof a surfactant for copper-catalyzed coupling reaction of arylboronic acids with imidazoles in water2012

    • Author(s)
      Kiyofumi Inamoto, Kanako Nozawa, JunKadokawa, Yoshinori Kondo
    • Journal Title

      Tetrahedron

      Volume: 68 Issue: 38 Pages: 7794-7798

    • DOI

      10.1016/j.tet.2012.07.042

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 3-carboxylated indoles through a tandem process involving cyclization of 2-ethynylanilines followed by CO2 fixation in the absence of transition metal catalysists2012

    • Author(s)
      K. Inamoto, N. Asano, Y. Nakamura, M. Yonemoto, Y. Kondo
    • Journal Title

      Organic Letters

      Volume: 14 Issue: 10 Pages: 2622-2625

    • DOI

      10.1021/ol300958c

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A copper-based catalytic system for carboxylation of terminal alkynes: synthesis of alkyl 2-alkynoates2012

    • Author(s)
      K. Inamoto, N. Asano, K. Kobayashi, M. Yonemoto, Y. Kondo
    • Journal Title

      Organic & Biomelecular Chemistry

      Volume: 10 Issue: 8 Pages: 1514-1516

    • DOI

      10.1039/c2ob06884b

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Micellar system in copper-catalyzed hydroxylation of arylboronic acids : facile access to phenols2011

    • Author(s)
      K.Inamoto, K.Nozawa, M.Yonemoto, Y.Kondo
    • Journal Title

      Chemical Communications

      Volume: 47 Issue: 42 Pages: 11775-11777

    • DOI

      10.1039/c1cc14974a

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Functionalization of heteroaromatic-N-oxides using organic superbase catalyst2011

    • Author(s)
      Y.Araki, K.Kobayashi, M.Yonemoto, Y.Kondo
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 9 Issue: 1 Pages: 78-80

    • DOI

      10.1039/c0ob00740d

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] トリフルオロメチルトリアルキルシランを用いた芳香族ケイ素化反応2016

    • Author(s)
      大澤沙優里、佐々木碧、熊田佳菜子、根東義則
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2016-03-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] DMPUによるトリフルオロメチルシランの活性化を経由した末端アルキンのケイ素化反応の開発2016

    • Author(s)
      稲木萌翔、熊田佳菜子、根東義則
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2016-03-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] 系内発生アミド塩基による芳香族複素環化合物の触媒的脱プロトン化修飾反応2016

    • Author(s)
      藤井悠光、熊田佳菜子、根東義則
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2016-03-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] アンモニウム塩を用いたラジカル的クロスカップリング反応によるビアリール骨格の構築2016

    • Author(s)
      甲斐佑典、Denneval Charline、熊田佳菜子、根東義則
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2016-03-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] Selective Functionalization of aromatics and heteroaromatics using organocatalytic systems2015

    • Author(s)
      根東義則
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Hilton Hawaiian Village, Honolulu, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 銅触媒C(sp3)-H結合官能基化を用いたイソインドリノン骨格構築法の開発2015

    • Author(s)
      亀山雄大、門川純、熊田佳菜子、根東義則
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      早稲田大学国際会議場
    • Year and Date
      2015-11-19
    • Related Report
      2015 Annual Research Report
  • [Presentation] シリルボランを用いたカルバゾール合成法の開発2015

    • Author(s)
      阿部将大、熊田佳菜子、根東義則
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      早稲田大学国際会議場
    • Year and Date
      2015-11-19
    • Related Report
      2015 Annual Research Report
  • [Presentation] 銅触媒C(sp3)-H結合官能基化を用いたイソインドリノン合成法の開発2015

    • Author(s)
      熊田佳菜子、亀山雄大、門川純、根東義則
    • Organizer
      第108回有機合成シンポジウム
    • Place of Presentation
      早稲田大学国際会議場
    • Year and Date
      2015-11-05
    • Related Report
      2015 Annual Research Report
  • [Presentation] トリフルオロメチルアルキルシランを利用したC-H結合ケイ素化反応2015

    • Author(s)
      熊田佳菜子、佐々木碧、大澤沙優里、稲木萌翔、根東義則
    • Organizer
      第41回反応と合成の進歩シンポジウム
    • Place of Presentation
      近畿大学11月ホール
    • Year and Date
      2015-10-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] 銅触媒を用いたイソインドリノン骨格合成法の開発2015

    • Author(s)
      亀山雄大、門川純、熊田佳菜子、根東義則
    • Organizer
      第54回日本薬学会東北支部大会
    • Place of Presentation
      岩手医科大学
    • Year and Date
      2015-09-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] シリルボランを用いた2-ニトロビアリール類の分子内C-Hアミノ化反応の開発2015

    • Author(s)
      阿部将大、熊田佳菜子、根東義則
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸
    • Year and Date
      2015-03-26 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] 有機超電子供与剤を用いたニトロベンゼン誘導体の変換反応2015

    • Author(s)
      安部瑛里奈、熊田佳菜子、根東義則
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸
    • Year and Date
      2015-03-26 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] アンモニウム塩を用いたカップリング反応によるヘテロビアリール骨格の構築2014

    • Author(s)
      山田哲也、根東義則
    • Organizer
      第40回反応と合成の進歩シンポジウム
    • Place of Presentation
      仙台
    • Year and Date
      2014-11-10 – 2014-11-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] フッ化オニウムを用いる芳香族ハロゲン化合物の脱ハロゲン化修飾反応2014

    • Author(s)
      中村亘佑、根東義則
    • Organizer
      第40回反応と合成の進歩シンポジウム
    • Place of Presentation
      仙台
    • Year and Date
      2014-11-10 – 2014-11-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] トリフルオロメチルシランを用いた芳香族複素環化合物のケイ素化反応2014

    • Author(s)
      佐々木碧、根東義則
    • Organizer
      第44回複素環化学討論会
    • Place of Presentation
      札幌
    • Year and Date
      2014-09-11 – 2014-09-12
    • Related Report
      2014 Annual Research Report
  • [Presentation] Madelung型インドール合成の触媒的閉環プロセスの開発2014

    • Author(s)
      阿部将大、稲本浄文、根東義則
    • Organizer
      日本薬学会第134年会
    • Place of Presentation
      熊本大学黒髪キャンパス
    • Related Report
      2013 Annual Research Report
  • [Presentation] 芳香族ハロゲン化合物のメタルフリー脱ハロゲン化反応2014

    • Author(s)
      中村亘佑、佐々木碧、吉川晶子、根東義則
    • Organizer
      日本薬学会第134年会
    • Place of Presentation
      熊本大学黒髪キャンパス
    • Related Report
      2013 Annual Research Report
  • [Presentation] オニウムアミド塩基を用いたC(sp3)-H脱プロトン化-修飾反応の開発2013

    • Author(s)
      稲本浄文、種田宏、吉川晶子、根東義則
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2013-03-27
    • Related Report
      2012 Annual Research Report
  • [Presentation] ルテニウム触媒C-Hカルボニル化を利用したジベンゾピラン骨格の新規合成法の開発2013

    • Author(s)
      稲本浄文、門川純、吉川晶子、根東義則
    • Organizer
      第52回日本薬学会東北支部大会
    • Place of Presentation
      東北大学川内キャンパス
    • Related Report
      2013 Annual Research Report
  • [Presentation] 芳香族ケイ素化合物のカルボキシル化反応2013

    • Author(s)
      小林みさと、稲本浄文、根東義則
    • Organizer
      第52回日本薬学会東北支部大会
    • Place of Presentation
      東北大学川内キャンパス
    • Related Report
      2013 Annual Research Report
  • [Presentation] オニウムアミド塩基を用いた触媒的C(sp3)-H脱プロトン化-修飾反応の開発2013

    • Author(s)
      稲本浄文、種田宏、吉川晶子、根東義則
    • Organizer
      第39回反応と合成の進歩シンポジウム
    • Place of Presentation
      九州大学医学部百年講堂
    • Related Report
      2013 Annual Research Report
  • [Presentation] オニウムアミド塩基による触媒的脱プロトン化-修飾反応の開発2012

    • Author(s)
      稲本浄文、大川ひとみ、佐藤菜央美、種田宏、廣野佑太郎、米本みさと、吉川晶子、根東義則
    • Organizer
      第38回反応と合成の進歩シンポジウム
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2012-11-05
    • Related Report
      2012 Annual Research Report
  • [Presentation] フッ化オニウムによるアミノシランの活性化を介した芳香複素環の修飾反応2012

    • Author(s)
      大川ひとみ、廣野佑太郎、米本みさと、吉川晶子、稲本浄文、根東義則
    • Organizer
      第51回日本薬学会東北支部大会
    • Place of Presentation
      青森大学薬学部
    • Year and Date
      2012-10-07
    • Related Report
      2012 Annual Research Report
  • [Presentation] フッ化物の添加による有機亜鉛試薬の活性化と反応2012

    • Author(s)
      藤村英範、米本みさと、吉川晶子、稲本浄文、根東義則
    • Organizer
      第51回日本薬学会東北支部大会
    • Place of Presentation
      青森大学薬学部
    • Year and Date
      2012-10-07
    • Related Report
      2012 Annual Research Report
  • [Presentation] オニウム塩触媒を用いる選択的分子変換反応2011

    • Author(s)
      米本みさと、荒木勇太、廣野佑太郎、大川ひとみ、佐藤菜緒美、稲本浄文、根東義則
    • Organizer
      第37回反応と合成の進歩シンポジウム
    • Place of Presentation
      徳島
    • Year and Date
      2011-11-07
    • Related Report
      2011 Annual Research Report
  • [Remarks] 分子変換化学分野ホームページ

    • URL

      http://www.pharm.tohoku.ac.jp/~henkan/lab/henkan_top.html

    • Related Report
      2015 Annual Research Report
  • [Remarks] 分子変換化学分野

    • URL

      http://www.pharm.tohoku.ac.jp/~henkan/lab/henkan_top.html

    • Related Report
      2014 Annual Research Report 2012 Annual Research Report
  • [Remarks] 分子変換化学分野

    • URL

      http://www.pharm.tohoku.ac.jp/~henkan/lab/henkan_top.html

    • Related Report
      2013 Annual Research Report
  • [Remarks]

    • URL

      http://www.pharm.tohoku.ac.jp/~henkan/lab/henkan_top.html

    • Related Report
      2011 Annual Research Report

URL: 

Published: 2011-08-01   Modified: 2019-07-29  

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