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Chiral polymer of cinchona alkaloid - peptide hybrid catalyst

Research Project

Project/Area Number 15K05517
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Polymer chemistry
Research InstitutionToyohashi University of Technology

Principal Investigator

Itsuno Shinichi  豊橋技術科学大学, 工学(系)研究科(研究院), 教授 (50158755)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Keywordsキラル高分子 / シンコナアルカロイド / スルホンアミド / スクアラミド / シンコナーペプチドハイブリッド / 有機分子触媒 / シンコナ-ペプチドハイブリッド / 高分子触媒 / ペプチド / 溝呂木-Heck反応
Outline of Final Research Achievements

Cinchona alkaloid-peptide hybrid catalysts were established. Chiral squaramidess containing aminated cinchona alkaloid and peptide were prepared. These hybrid catalysts showed high level of stereoselectivities in asymmetric Michael reactions. Cinchona alkaloids contain vinyl group in their molecules. When iodophenyl group was introduced onto the hybrid catalyst, Heck coupling reaction occurred between the hybrid catalyst molecules to form chiral polymers. This is the first synthesis of chiral cinchona squaramide polymer. The polymeric chiral squaramides were used as catalysts in various asymmetric synthesis and showed excellent catalytic performances. In some cases, the polymeric catalysts showed higher stereoselectivity compared to the corresponding low-molecular hybrid catalysts. Since the polymeric catalysts we have developed are insoluble in commonly used organic solvents, the polymeric catalysts were easily recovered and reused many times.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (49 results)

All 2018 2017 2016 2015 Other

All Journal Article (11 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 11 results,  Open Access: 2 results,  Acknowledgement Compliant: 6 results) Presentation (30 results) (of which Int'l Joint Research: 18 results,  Invited: 7 results) Book (6 results) Remarks (1 results) Funded Workshop (1 results)

  • [Journal Article] Cinchona Squaramide-Based Chiral Polymers as Highly Efficient Catalysts in Asymmetric Michael Addition Reaction2018

    • Author(s)
      Ullah Mohammad Shahid、Itsuno Shinichi
    • Journal Title

      ACS Omega

      Volume: 3 Issue: 4 Pages: 4573-4582

    • DOI

      10.1021/acsomega.8b00398

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthsis of main-chain ionic polymer of Chiral Imidazolidinone Organocatalysts and Their Application to Asymmetric Diels-Alder Reaction2018

    • Author(s)
      Naoki Haraguchi, Nagisa Takenaka, Aisyah Najwa, and Nguyen Tanh Liem and Shinichi Itsuno.
    • Journal Title

      Adv. Synth. Catal.

      Volume: 360 Issue: 1 Pages: 112-123

    • DOI

      10.1002/adsc.201701016

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of chiral polyesters of cinchona alkaloid catalysts for enantioselective Michael addition of anthrone to nitroalkenes2018

    • Author(s)
      Kumpuga Bahati Thom、Itsuno Shinichi
    • Journal Title

      Journal of Catalysis

      Volume: 361 Pages: 398-406

    • DOI

      10.1016/j.jcat.2018.03.020

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of cinchona alkaloid squaramide polymers as bifunctional chiral organocatalysts for the enantioselective michael addition of β-ketoesters to nitroolefins2017

    • Author(s)
      Ullah Mohammad Shahid、Itsuno Shinichi
    • Journal Title

      Molecular Catalysis

      Volume: 438 Pages: 239-244

    • DOI

      10.1016/j.mcat.2017.06.010

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polyesters Containing Chiral Imidazolidinone Salts in Polymer Main Chain: Heterogeneous Organocatalysts for Asymmetric Diels-Alder Reaction2017

    • Author(s)
      Naoki Haraguchi, Liem Nguyen Tanh and Shinichi Itsuno.
    • Journal Title

      ChemCatChem

      Volume: 9 Issue: 19 Pages: 3786-3794

    • DOI

      10.1002/cctc.201700723

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Chiral Polyamides Containing an (R,R)-1,2-Diphenylethylenediamine Monosulfonamide Structure and Their Application to Asymmetric Transfer Hydrogenation Catalysis2017

    • Author(s)
      Itsuno, S.; Takahashi, S.
    • Journal Title

      ChemCatChem

      Volume: 9 Issue: 3 Pages: 385-388

    • DOI

      10.1002/cctc.201700122

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] "Highly active polymeric organocatalyst: Chiral ionic polymers prepared from 10, 11‐didehydrogenated cinchonidinium salt2016

    • Author(s)
      Md. Mehadi Hassan, Naoki Haraguchi, and Shinichi Itsuno
    • Journal Title

      J. Polym. Sci. Part A: Polym. Chem.

      Volume: 54 Issue: 5 Pages: 621-627

    • DOI

      10.1002/pola.27905

    • Related Report
      2016 Research-status Report 2015 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Synthesis of Cinchona Alkaloid Sulfonamide Polymers as Sustainable Catalysts for the Enantioselective Desymmetrization of Cyclic Anhydrides2016

    • Author(s)
      Takata, S.; Endo, Y.; Ullah, M. S.; Itsuno, S.
    • Journal Title

      RSC Advanced

      Volume: 6 Issue: 76 Pages: 72300-72305

    • DOI

      10.1039/c6ra14535c

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Protein Folding Structures: Formation of Folding Structures Based on Probability Theory2016

    • Author(s)
      Narita, M.; Narita, M.; Itsuno, Y.; Itsuno, S.
    • Journal Title

      ACS Omega

      Volume: 1 Issue: 6 Pages: 1355-1366

    • DOI

      10.1021/acsomega.6b00206

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] キラル高分子触媒の合成と不斉反応への応用2016

    • Author(s)
      伊津野 真一
    • Journal Title

      有機合成化学協会誌

      Volume: 74 Pages: 710-719

    • NAID

      130005253389

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Chiral Polyethers Containing Imidazolidinone Repeating Units and Application as Catalyst in Asymmetric Diels-Alder Reaction2015

    • Author(s)
      Shinichi Itsuno, Tatsuaki Oonami, Nagisa Takenaka, and Naoki Haraguchi
    • Journal Title

      Adv. Synth. Catal.

      Volume: 357 Issue: 18 Pages: 3995-4002

    • DOI

      10.1002/adsc.201500539

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] シンコナアルカロイド-ペプチドハイブリッド触媒の合成と 不斉反応への応用2018

    • Author(s)
      久保侑輝、伊津野 真一
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 主鎖にペプチドを組み込んだシンコナアルカロイドスクアラミド高分子の合成と不斉反応への応用2017

    • Author(s)
      権田裕樹、Nor Zawanie, 原口直樹、伊津野 真一
    • Organizer
      第48回中部化学関係学協会支部連合秋季大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] シンコナアルカロイド構造を有する高分子ミクロスフェアを用いた不斉反応2017

    • Author(s)
      古橋春花、藤沢郁英、原口直樹、伊津野 真一
    • Organizer
      第48回中部化学関係学協会支部連合秋季大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis of cinchona-based chiral polyester catalysts for sustainable process of asymmetric reactions2017

    • Author(s)
      Kumpuga Bahati Thom, 伊津野 真一
    • Organizer
      Chirality 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of chiral polymers containing cinchona alkaloid derived organocatalyst in their main chain2017

    • Author(s)
      伊津野 真一
    • Organizer
      International Symposium on Pure and Applied Chemistry 2017 (ISPAC 2017)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of cinchona-based squaramide polymer catalysts for sustainable process of asymmetric reactions2017

    • Author(s)
      伊津野 真一
    • Organizer
      2nd Green and Sustainable Chemistry Conference
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of chiral polymers and their applications to asymmetric catalysis2017

    • Author(s)
      伊津野 真一
    • Organizer
      Mukarram Hussain Khundkar (MHK) Memorial Lecture
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Cinchona Alkaloid Squaramide Polymers as Bifunctional Chiral Organocatalysts for the Enantioselective Michael Addition of beta-Ketoester to Nitroolefin2016

    • Author(s)
      Mohammad Shahid Ullah, Naoki Haraguchi, and Shinichi Itsuno
    • Organizer
      The 11th SPSJ International Polymer Conference
    • Place of Presentation
      福岡
    • Year and Date
      2016-12-13
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of chiral polymer catalysts and their application to asymmetric reactions2016

    • Author(s)
      Itsuno, S.
    • Organizer
      SmaSys 2016
    • Place of Presentation
      米沢
    • Year and Date
      2016-10-13
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 高度な不斉触媒活性を有するキラル高分子の合成と不斉反応への応用2016

    • Author(s)
      伊津野真一
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Synthesis of chiral polymer catalysts and their application to asymmetric reactions2016

    • Author(s)
      伊津野真一
    • Organizer
      高分子コロキウム
    • Place of Presentation
      福島
    • Year and Date
      2016-09-09
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Highly Active Chiral Polymer Catalyst for Asymmetric Reactions2016

    • Author(s)
      Shinichi Itsuno, Yuta Endo, Shohei Takata, Md. Shahid Ullah
    • Organizer
      Chirality 2016
    • Place of Presentation
      Heidelberg
    • Year and Date
      2016-07-24
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of main-chain polyesters having MacMillan catalyst for asymmetric Diels-Alder reaction2016

    • Author(s)
      Nguyen Thanh Liem, Naoki Haraguchi, and Shinichi Itsuno
    • Organizer
      Chirality 2016
    • Place of Presentation
      Heidelberg
    • Year and Date
      2016-07-24
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] 殿重合を用いたスルホン酸を有する高分子微粒 子の合成2016

    • Author(s)
      油谷 海斗 ・原口 直樹 ・伊津野 真一
    • Organizer
      高分子学会第65年次大会
    • Place of Presentation
      神戸
    • Year and Date
      2016-05-25
    • Related Report
      2016 Research-status Report
  • [Presentation] スルホンアミド構造を有するシンコナアルカロイド高 分子の合成と不斉 Michael 付加反応への応用2016

    • Author(s)
      遠藤 祐 太 ・原口 直樹 ・伊津野 真一
    • Organizer
      高分子学会第65年次大会
    • Place of Presentation
      神戸
    • Year and Date
      2016-05-25
    • Related Report
      2016 Research-status Report
  • [Presentation] キラルピロリジン触媒を有する高分子微粒子の合成と不斉 Michael 付加反応への応用2016

    • Author(s)
      小野 裕也 ・大山 和子 ・原口 直樹 ・伊津野 真一
    • Organizer
      高分子学会第65年次大会
    • Place of Presentation
      神戸
    • Year and Date
      2016-05-24
    • Related Report
      2016 Research-status Report
  • [Presentation] キラルイミダゾリジノンを主鎖骨格に有するキラル 高分子の合成と不斉 Diels-Alder 反応への応用2016

    • Author(s)
      グエン タンリエム ・原口 直樹 ・伊津野 真一
    • Organizer
      高分子学会第65年次大会
    • Place of Presentation
      神戸
    • Year and Date
      2016-05-24
    • Related Report
      2016 Research-status Report
  • [Presentation] ynthesis of Main-Chain Polymers of Chiral Imidazolidinone Salt and Their Application for Asymmetric Organocatalysis,2016

    • Author(s)
      Naoki Haraguchi, Nagisa Takenaka, Tatsuaki Onami, and Shinichi Itsuno
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      大阪
    • Year and Date
      2016-04-20
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] ynthesis of Cinchona Alkaloid Polymers Containing Squaramide Structure and Their Application to Asymmetric Reaction2016

    • Author(s)
      Nor Zawanie, Naoki Haraguchi, Shinichi Itsuno
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      大阪
    • Year and Date
      2016-04-20
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Main-Chain Polymers of Chiral Imidazolidinone Salt and Their Application for Asymmetric Organocatalysis2016

    • Author(s)
      Naoki Haraguchi, Nagisa Takenaka, Tatsuaki Onami, and Shinichi Itsuno, Osaka, Japan 2016/4/20-22
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      大阪
    • Year and Date
      2016-04-20
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Cinchona Alkaloid Polymers Containing Squaramide Structure and Their Application to Asymmetric Reaction2016

    • Author(s)
      Nor Zawanie, Naoki Haraguchi, and Shinichi Itsuno
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      大阪
    • Year and Date
      2016-04-20
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of cinchona alkaloid polymer catalysts for sustainable process of asymmetric reactions2016

    • Author(s)
      Shinichi Itsuno, Md. Shahid Ullah
    • Organizer
      Green & Sustainable Chemistry
    • Place of Presentation
      Berlin
    • Year and Date
      2016-04-03
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of cinchona alkaloid polymer catalysts for sustainable process of asymmetric reactions2016

    • Author(s)
      Shinichi Itsuno
    • Organizer
      Green & Sustainable Chemistry Conference
    • Place of Presentation
      Berlin, Germany
    • Year and Date
      2016-04-03
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] TsDPEN構造を主鎖に組み込んだ高分子キラルリガンドの合成と不斉触媒への応用2016

    • Author(s)
      髙橋 昌太郎、原口 直樹、伊津野 真一   2016年3月24日-27日
    • Organizer
      日本化学会第96回春季大会
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] スルホンアミド型シンコナアルカロイドを主鎖骨格に有する高分子の合成と不斉反応への応用2016

    • Author(s)
      高田 翔平、原口 直樹、伊津野 真一
    • Organizer
      日本化学会第96回春季大会
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] MacMillan触媒を主鎖骨格に有する イオン結合型高分子の合成と不斉反応への応用(IX)2016

    • Author(s)
      竹中 渚、原口 直樹、伊津野 真一
    • Organizer
      日本化学会第96回春季大会
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Design of Chiral Polymer Organocatalysts Derived from Cinchona Alkaloid and Amino Acid2016

    • Author(s)
      Itsuno, S.
    • Organizer
      NCKU Chemistry Seminar
    • Place of Presentation
      台南
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Development of main-chain polymer of chiral organocatalyst for asymmetric reaction2015

    • Author(s)
      Naoki Haraguchi and Shinichi Itsuno
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Hawaii, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Chiral Polymers of Cinchona Derived Organocatalyst and their Application to Asymmetric Catalysis2015

    • Author(s)
      Shinichi Itsuno
    • Organizer
      International Symposium on Organic Chemistry
    • Place of Presentation
      Kuala Lumpur,b Malaysia
    • Year and Date
      2015-09-21
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of chiral polymers containing imidazolidinone repeating unit and their application to asymmetric catalysis2015

    • Author(s)
      Shinichi Itsuno
    • Organizer
      Chirality 2015
    • Place of Presentation
      Boston, USA
    • Year and Date
      2015-06-28
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Book] Science of Synthesis2017

    • Author(s)
      Itsuno, S. and Ullah, M. S.
    • Total Pages
      40
    • Publisher
      Thieme
    • Related Report
      2016 Research-status Report
  • [Book] Boron Reagents in Synthesis2016

    • Author(s)
      Itsuno, S.
    • Total Pages
      34
    • Publisher
      ACS
    • Related Report
      2016 Research-status Report
  • [Book] CSJカレントレビュー, 有機分子触媒の化学2016

    • Author(s)
      原口 直樹、伊津野 真一
    • Total Pages
      4
    • Publisher
      化学同人
    • Related Report
      2016 Research-status Report
  • [Book] Boron Reagents in Synthesis2016

    • Author(s)
      Shinichi Itsuno
    • Total Pages
      44
    • Publisher
      American Chemical Society
    • Related Report
      2015 Research-status Report
  • [Book] Encyclopedia of Polymeric Nanomaterials2015

    • Author(s)
      Shinichi Itsuno
    • Total Pages
      10
    • Publisher
      Springer
    • Related Report
      2015 Research-status Report
  • [Book] 元素ブロック材料:有機‐無機ハイブリッド材料の新概念2015

    • Author(s)
      伊津野真一
    • Total Pages
      8
    • Publisher
      CMC出版
    • Related Report
      2015 Research-status Report
  • [Remarks] Eurekalert

    • URL

      https://www.eurekalert.org/pub_releases/2016-10/tuot-aef101416.php

    • Related Report
      2016 Research-status Report
  • [Funded Workshop] International Symposium on Organic Chemistry2015

    • Place of Presentation
      Kuala Lumpur, Malaysia
    • Year and Date
      2015-09-21
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2019-03-29  

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