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Development of Dynamic Asymmetric Organocatalysis and Their Mechanistic Studies

Research Project

Project/Area Number 22750084
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe Institute of Physical and Chemical Research (2011)
Tokyo University of Agriculture and Technology (2010)

Principal Investigator

SOHTOME Yoshihiro  独立行政法人理化学研究所, 袖岡有機合成化学研究室, 研究員 (50431888)

Project Period (FY) 2010 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2010: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Keywords有機触媒 / 不斉合成 / 水素結合 / エントロピー / マイケル反応 / フェノール / 不斉触媒 / グアニジン / チオウレア / エンタルピー
Research Abstract

We have designed and developed 1, 3-diamine-tethered guanidine/bisthiourea organocatalysts for catalytic asymmetric 1, 4-additions including 1) Friedel-Crafts alkylation of phenols and 2) phospha-Michael reactions. Kinetic analyses using Eyring plots uncovered that differences in the activation entropies(ΔΔS^‡) play a principal role in the stereodiscrimination of the developed F-C reactions. We also found that, in the phospha-Michael reactions, either the monomeric or oligomeric active species of the catalyst can be utilized depending on the solvent system.

Report

(3 results)
  • 2011 Annual Research Report   Final Research Report ( PDF )
  • 2010 Annual Research Report
  • Research Products

    (33 results)

All 2012 2011 2010

All Journal Article (16 results) (of which Peer Reviewed: 15 results) Presentation (15 results) Book (2 results)

  • [Journal Article] Organocatalytic Asymmetric Synthesis of N, N-Bis-Dihydrofuranyl-Hydroxyamines : A Cascade Reaction Involving Friedel-Crafts Alkylation, Internal Redox Reaction and Umpolung2011

    • Author(s)
      Yoshihiro Sohtome, Takahisa Yamaguchi, Bongki Shin, Kazuo Nagasawa
    • Journal Title

      Chem. Lett

      Volume: 40 Pages: 843-845

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Phospha-Michael Reaction of Diphenyl Phosphite with Nitroolefins Utilizing Conformationally Flexible Guanidine/Bisthiourea Organocatalyst : Assembly-State Tunability in Asymmetric Organocatalysis2011

    • Author(s)
      Yoshihiro Sohtome, Natsuko Horitsugi, Rika Takagi, Kazuo Nagasawa
    • Journal Title

      Adv. Synth. Catal.

      Volume: 353 Pages: 2631-2636

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Linking the Conformational Flexibility and Kinetics : Catalytic 1, 4-Type Friedel-Crafts Reaction of Phenols Utilizing 1, 3-Diamine-Tethered-Guanidine/Bisthiourea Organocatalysts2011

    • Author(s)
      Yoshihiro Sohtome, Bongki Shin, Natsuko Horitsugi, Keiichi Noguchi, Kazuo Nagasawa
    • Journal Title

      Chem. Asian. J.

      Volume: 6 Pages: 2463-2470

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Organocatalytic Asymmetric Synthesis of N,N-Bis-dihydrofuranyl-hydroxyamines : A Cascade Reaction Involving Friedel-Crafts Alkylation, Internal Redox Reaction and Umpolung2011

    • Author(s)
      Yoshihiro Sohtome, Bongki Shin, Takahisa Yamaguchi, Kazuo Nagasawa
    • Journal Title

      Chem.Lett.

      Volume: 40 Pages: 843-845

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Phospha-Michael Reaction of Diphenyl Phosphite with Nitroolefins Utilizing Conformationally Flexible Guanidine/Bisthiourea Organocatalyst : Assembly-State Tunability in Asymmetric Organocatalysis2011

    • Author(s)
      Yoshihiro Sohtome, Natsuko Horitsugi, Rika Takagi, Kazuo Nagasawa
    • Journal Title

      Adv.Synth.Catal

      Volume: 353 Issue: 14-15 Pages: 2631-2636

    • DOI

      10.1002/adsc.201100219

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Linking the Conformational Flexibility and Kinetics : Catalytic 1,4-Type Friedel-Crafts Reactions of Phenols Utilizing 1,3-Diamine-Tethered-Guanidine/Bisthiourea Organocatalysts2011

    • Author(s)
      Yoshihiro Sohtome, Bongki Shin, Natsuko Horitsugi, Keiichi Noguchi, Kazuo Nagasawa
    • Journal Title

      Chem.Asian J.

      Volume: 6 Issue: 9 Pages: 2463-2470

    • DOI

      10.1002/asia.201100363

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dynamic Enantiodivergent Organocatalysis : Merging Molecular Motors with Bifunctional Organocatalysts2011

    • Author(s)
      Yoshihiro Sohtome, Kazuo Nagasawa
    • Journal Title

      ChemPhysChem

      Volume: 12 Issue: 12 Pages: 2217-2219

    • DOI

      10.1002/cphc.201100335

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] フレキシブルな有機触媒を用いる不斉反応2011

    • Author(s)
      五月女宜裕
    • Journal Title

      化学と工業

      Volume: 64 Pages: 789-789

    • NAID

      10029684190

    • Related Report
      2011 Annual Research Report
  • [Journal Article] Linking the Conformational Fleibility and Kinetics : Catalytic 1,4-Type Friedel-Crafts Reactions of Phenols Utilizing 1,3-Diamine-Tethered-Guanidine/Bisthiourea Organocatalysts2011

    • Author(s)
      Yoshihiro Sohtome, Bongki Shin, Natsuko, Horitsugi, Keiichi Noguchi, Kazuo Nagasawa
    • Journal Title

      Chem.Asian.J.

      Volume: (in press)

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Solvent-Dependent Enantiodivergent Mannich-Type Reaction : Utilizing Conformational Flexible Guanidine/Bisthiourea Organocatalyst2010

    • Author(s)
      Yoshihiro Sohtome, Shinji Tanaka, Keisuke Takada, Takahisa, Yamaguchi, Kazuo Nagasawa
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 49 Pages: 9254-9257

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Entropy-Controlled Catalytic Asymmetric 1, 4-Type Friedel-Crafts Reaction of Phenols Using A Conformationally Flexible Guanidine/Bisthiourea Organocatalyst2010

    • Author(s)
      Yoshihiro Sohtome, Shin Bongki, Natsuko Horitsugi, Rika Takagi, Keiichi Noguchi, Kazuo Nagasawa
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 49 Pages: 7299-7303

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] The Design of Chiral Double Hydrogen Bonding Networks and Their Applications to Catalytic Asymmetric Carbon. Carbon and Carbon. Oxgen Bond. Forming Reactions2010

    • Author(s)
      Yoshihiro Sohtome, Kazuo Nagasawa
    • Journal Title

      Synlett

      Pages: 1-22

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Solvent-Dependent Enantiodivergent Mannich-Type Reaction : Utilizing a Conformationally Flexible Guanidine/Bisthiouea Organocatalyst2010

    • Author(s)
      Yoshihiro Sohtome, Shinji Tanaka, Keisuke Takada, Takahisa Yamaguchi, Kazuo Nagasawa
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 49 Pages: 9254-9257

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Entropy-Controlled Catalytic Asymmetric 1,4-Type Friedel-Crafts Reaction of Phenols Using Conformationally Flexible Guanidine/Bisthiourea Organocatalyst2010

    • Author(s)
      Yoshihiro Sohtome, Bongki Shin, Natsuko, Horitsugi, Rika Takagi, Keiichi Noguchi, Kazuo Nagasawa
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 49 Pages: 7299-7303

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Design of Chiral Double Hydrogen Bonding Networks and Their Applications to Catalytic Asymmetric Carbon-Carbon and Carbon-Oxygen Bond-Forming Reactions2010

    • Author(s)
      Yoshihiro Sohtome, Kazuo Nagasawa
    • Journal Title

      Synlett

      Pages: 1-22

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 不斉触媒が切り拓くリード化合物の構造展開2010

    • Author(s)
      五月女宜裕
    • Journal Title

      フアルマシア

      Volume: 46 Pages: 268-269

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] 鎖状グアニジニン/チオウレア触媒の分子設計に基づく触媒機能の開拓研究2012

    • Author(s)
      五月女宜裕
    • Organizer
      第25回若い世代の特別講演会(日本化学会第91春季年会)
    • Place of Presentation
      慶応義塾大学理工学部
    • Year and Date
      2012-03-25
    • Related Report
      2011 Final Research Report
  • [Presentation] 鎖状グアニジン/チオウレア触媒の分子設計に基づく触媒機能の開拓研究2012

    • Author(s)
      五月女宜裕
    • Organizer
      第25回若い世代の特別講演会、日本化学会第92春季年会
    • Place of Presentation
      神奈川県、横浜市、慶応義塾大学理工学部(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] 環境応答性有機触媒の多次元制御2011

    • Author(s)
      五月女宜裕
    • Organizer
      理研シンポジウム
    • Place of Presentation
      理化学研究所、鈴木梅太郎ホール
    • Year and Date
      2011-07-01
    • Related Report
      2011 Final Research Report
  • [Presentation] 環境応答性有機触媒の多次元制御2011

    • Author(s)
      五月女宜裕
    • Organizer
      理研シンポジウム
    • Place of Presentation
      埼玉県、和光市、理化学研究所、鈴木梅太郎ホール(招待講演)
    • Year and Date
      2011-07-01
    • Related Report
      2011 Annual Research Report
  • [Presentation] 鎖状グアニジン/チオウレア触媒の分子設計に基づく触媒機能の開拓研究2011

    • Author(s)
      五月女宜裕
    • Organizer
      第25回若い世代の特別講演会(日本化学会第91春季年会)
    • Place of Presentation
      (招待講演 日本化学会第91春季年会(2011)講演予稿集)
    • Year and Date
      2011-03-11
    • Related Report
      2010 Annual Research Report
  • [Presentation] 鎖状グアニジン/チオウレア触媒を用いるフェーノール類の触媒的不斉フリーデル/クラフツ反応におけるメカニズム解析2011

    • Author(s)
      五月女宜裕
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      (日本化学会第91春季年会(2011)講演予稿集)
    • Year and Date
      2011-03-11
    • Related Report
      2010 Annual Research Report
  • [Presentation] Asymmetric Cycle-Specific Catalysis Utilizing a 1, 3-Diamine-Tethered Guanidine/Bisthiourea Organocatalyst2011

    • Author(s)
      Yoshihiro Sohtome, Kazuo Nagasawa
    • Organizer
      The 6th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      Hong Kong, The Chinese University of Hong Kong
    • Related Report
      2011 Final Research Report
  • [Presentation] 1, 3-ジアミン型グアニジン/ビスチオウレア触媒の創製:触媒的不斉Friedel-Crafts反応及びカスケード反応への展開2011

    • Author(s)
      五月女宜裕、山口昂久、堀次奈津子、申峰基、長澤和夫
    • Organizer
      第37回反応と合成の進歩シンポジウム
    • Place of Presentation
      徳島県あわぎんホール
    • Related Report
      2011 Final Research Report
  • [Presentation] 1,3-ジアミン型グアニジン/ビスチオウレア触媒の創製:触媒的不斉Friedel-Crafts反応及びカスケード反応への展開2011

    • Author(s)
      五月女宜裕、山口昂久、堀次奈津子、申峰基、長澤和夫
    • Organizer
      第37回反応と合成の進歩シンポジウム
    • Place of Presentation
      徳島県、徳島市、あわぎんホール
    • Related Report
      2011 Annual Research Report
  • [Presentation] Asymmetric Cycle-Specific Catalysis Utilizing a 1,3-Diamine-Tethered Guanidine/Bisthiourea Organocatalyst2011

    • Author(s)
      Yoshihiro Sohtome, Kazuo Nagasawa
    • Organizer
      The 6th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      Hong Kong、Sha Tin、The Chinese University of Hong Kong
    • Related Report
      2011 Annual Research Report
  • [Presentation] 多点水素結合ネットワークの分子設計に基づく触媒機能の開拓研究2010

    • Author(s)
      五月女宜裕
    • Organizer
      神戸大学大学院理学系研究科化学専攻、学術講演会
    • Place of Presentation
      兵庫県、神戸大学理学系研究科(招待講演)
    • Year and Date
      2010-10-02
    • Related Report
      2010 Annual Research Report
  • [Presentation] キラル水素結合ネットワークの分子設計:触媒的不斉反応への展開2010

    • Author(s)
      五月女宜裕
    • Organizer
      理研セミナー
    • Place of Presentation
      埼玉県、理化学研究所、物質科学棟(招待講演)
    • Year and Date
      2010-09-13
    • Related Report
      2010 Annual Research Report
  • [Presentation] Solvent-Dependent Enantiodivergent Mannich-Type Reaction Utilizing Conformationally Flexible Guanidine/Bisthiourea Organocatalyst2010

    • Author(s)
      Yoshihiro Sohotme, Shinji Tanaka, Kazuo Nagasawa
    • Organizer
      ISCD2010
    • Place of Presentation
      北海道、札幌コンベンションセンター
    • Year and Date
      2010-07-14
    • Related Report
      2011 Final Research Report 2010 Annual Research Report
  • [Presentation] 新規鎖状グアニジン/チオウレア触媒の創製:ニトロオレフィン類の触媒的不斉1, 4-付加反応2010

    • Author(s)
      五月女宜裕、申峰基、堀次奈津子、高城梨夏、長澤和夫
    • Organizer
      第97回有機合成シンポジウム
    • Place of Presentation
      慶應義塾大学薬学部
    • Year and Date
      2010-06-18
    • Related Report
      2011 Final Research Report
  • [Presentation] 新規鎖状グアニジン/チオウレア触媒の創製:ニトロオレフィン類の触媒的不斉1,4-付加反応2010

    • Author(s)
      五月女宜裕
    • Organizer
      第97回有機合成シンポジウム
    • Place of Presentation
      東京都、慶應義塾大学薬学部(芝共立キャンパス)
    • Year and Date
      2010-06-18
    • Related Report
      2010 Annual Research Report
  • [Book] Chiral Guanidine and Amidine Organocatalysts in Science of Synthesis Reference Library, Asymmetric Organocatalysis 2 ; Bronsted Base and Acid Catalysts, and additional Topics2012

    • Author(s)
      Kazuo Nagasawa, Yoshihiro Sohtome
    • Related Report
      2011 Final Research Report
  • [Book] Science of Synthesis, Asymmetric Organocatalysis 2 Bronsted Base and Acid Catalysts, and Additional Topics2012

    • Author(s)
      Kazuo Nagasawa, Yoshihiro Sohtome
    • Publisher
      George Thieme Verlag KG Stuttgart New-York
    • Related Report
      2011 Annual Research Report

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Published: 2010-08-23   Modified: 2016-04-21  

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