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2013 Fiscal Year Final Research Report

A Highly Efficient Method for the Synthesis of Nitrogen-containing Materials Using Umpolung Addition to Electron-Deficient Imines

Research Project

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Project/Area Number 23350040
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionMie University

Principal Investigator

SHIMIZU Makoto  三重大学, 工学(系)研究科(研究院), 教授 (30162712)

Project Period (FY) 2011-04-01 – 2014-03-31
Keywordsαーイミノエステル / 極性転換反応 / タンデム反応 / β,γ-不飽和-α-イミノエステル / α-アシロキシイミノエステル / N,N―ジアルキル化反応 / N,N.C―トリアルキル化反応 / ファインケミカルズ
Research Abstract

We have already reported that the N-alkylation reaction of alpha-iminoester proceeds using aluminum reagents to give the N-alkylation products in high yields. In the present project, we investigated highly regioselective N-alkylation of beta,gamma-alkenyl-alpha-iminoesters and subsequent directed vinylogous aldol reaction with in situ generated dienolates. It was also found that the sulfenyl group of the alkene part improved the selectivity of both steps, leading to the formation of 3-amino-2-pyrones by anti-elimination of thiols. Furthermore, on treatment with two different Grignard reagents, alpha-acyloxyimino esters gave the corresponding dialkylation products with different substituents on the nitrogen atom. N,N,C-Trialkylated products with all different substituents were obtained via the oxidation and the nucleophilic addition reaction to the resulting iminium salts.

  • Research Products

    (61 results)

All 2014 2013 2012 2011 Other

All Journal Article (26 results) (of which Peer Reviewed: 26 results) Presentation (32 results) Book (2 results) Remarks (1 results)

  • [Journal Article] Tandem N-Alkylation/Vinylogous Aldol Reaction of β,γ-Alkenyl α-Iminoester2014

    • Author(s)
      H. Tanaka, I. Mizota, M. Shimizu
    • Journal Title

      Org. Lett

      Volume: 16, (8) Pages: 2276-2279

    • Peer Reviewed
  • [Journal Article] 2-Aryl-4-quinolone Synthesis Using the Thermal Rearrangement of Iminocyclobutenones2014

    • Author(s)
      I. Hachiya, K. Yokoyama, A. Ito, M. Shimizu
    • Journal Title

      Heterocycles

      Volume: 90, (1)(in press)

    • Peer Reviewed
  • [Journal Article] Chemoselective Reductions and Iodinations Using Titanium Tetraiodide2014

    • Author(s)
      I. Hachiya, M. Shimizu
    • Journal Title

      Tetrahedron Lett

      Volume: 55, (17) Pages: 2781-2788

    • Peer Reviewed
  • [Journal Article] Chiral ・-Lactam Synthesis through the Enantioselective Reduction of Iminocyclobutenones and Thermal Rearrangement of Aminocyclobutenones2014

    • Author(s)
      I. Hachiya, A. Ito, M. Shimizu
    • Journal Title

      Asian J. Org. Chem

      Volume: 3(in press)

    • Peer Reviewed
  • [Journal Article] Titanium Tetraiodide Mediated Organic Reactions2014

    • Author(s)
      T. Haneishi, I. Hachiya, M. Shimizu
    • Journal Title

      Arabian J. Sci. Eng

      Volume: 39(in press)

    • Peer Reviewed
  • [Journal Article] Integrated Reactions Based on the Sequential Addition to α-Imino Esters2014

    • Author(s)
      K. Koyama, I. Mizota, M. Shimizu
    • Journal Title

      Pure Appl. Chem

      Volume: 86(in press)

    • Peer Reviewed
  • [Journal Article] Two-Step Synthesis of 3,4-Ethylenedioxythiophene (EDOT) from 2,3-Butanedione2014

    • Author(s)
      I. Hachiya, T. Yamamoto, T. Inagaki, T. Matsumoto, A. Takahashi, I. Mizota, M. Shimizu
    • Journal Title

      Heterocycles

      Volume: 88, (1) Pages: 607-612

    • Peer Reviewed
  • [Journal Article] Diastereoselective Iodo Aldol Reaction ofγ-Alkoxy αβ-Alkynyl Ketone Derivatives Promoted by Titnium Tetraiodide2013

    • Author(s)
      Tetraiodide,I. Hachiya, S. Ito, S. Kayaki, M. Shimizu
    • Journal Title

      Asian J. Org. Chem

      Volume: 2, (11) Pages: 931-934

    • Peer Reviewed
  • [Journal Article] Regioselective Tandem N-Alkylation/ C-Acylation of β,γ-Alkynyl α-Imino Esters2013

    • Author(s)
      Mizota, Y. Matsuda, S. Kamimura, H. Tanaka, M. Shimizu
    • Journal Title

      Org. Lett

      Volume: 15, (16) Pages: 4206-4209

    • Peer Reviewed
  • [Journal Article] Synthesis of Azulene Derivatives Having an Azathiacrown Ether Moiety and Their Selective Color Reaction toward Silver Ion2013

    • Author(s)
      S. Wakabayashi, M. Uchida, R. Tanaka, M. Shimizu
    • Journal Title

      Asian J. Org. Chem

      Volume: 2, (9) Pages: 786-791

    • Peer Reviewed
  • [Journal Article] Tandem N-Alkylation-Addition Reaction of α-Imino Esters and Application to a New Flow System2013

    • Author(s)
      T. Sano, I. Mizota, M. Shimizu
    • Journal Title

      Chem. Lett

      Volume: 42, (9) Pages: 995-997

    • Peer Reviewed
  • [Journal Article] Highly Diastereoselective Tandem N-Alkylation-Mannich Reaction of α-Imino Esters2013

    • Author(s)
      M. Shimizu, D. Kurita, I. Mizota
    • Journal Title

      Asian J. Org. Chem

      Volume: 2, (3) Pages: 208-211

    • Peer Reviewed
  • [Journal Article] A New Single-ion Polymer Electrolyte Based on Polyvinyl Alcohol for Lithium Ion Batteries2013

    • Author(s)
      Y. S. Zhu, X. J. Wang, Y. Y. Hou, X. W. Gao, L. L. Liu, Y. P. Wu, M. Shimizu
    • Journal Title

      Electrochimica Acta

      Volume: 87, (1) Pages: 113-118

    • Peer Reviewed
  • [Journal Article] Synthesis of Indolin-3-ones and Tetrahydro-4-quinolones Using α-Imino Esters2013

    • Author(s)
      M. Shimizu, Y. Takao, H. Katsurayama, I. Mizota
    • Journal Title

      Asian J. Org. Chem

      Volume: 2, (2) Pages: 130-134

    • Peer Reviewed
  • [Journal Article] Synthesis of α-Amino Ketones and O-Alkyloximes by Titanium Tetrahalide Promoted Ring-opening Reaction of 2-Mono-substitued Azetidine-3-ones and Their O-Alkyloximes2012

    • Author(s)
      S. Ariga, S. Hata, D. Fukuda, T. Nishi, I. Hachiya, M. Shimizu
    • Journal Title

      Heterocycles

      Volume: 86, (2) Pages: 1187-1210

    • Peer Reviewed
  • [Journal Article] Synthesis of α-Dialkylamino Esters Using Tandem N,N-Dialkylation of α-Sulfoximino Ester2012

    • Author(s)
      S. Hata, T. Maeda, M. Shimizu
    • Journal Title

      Bull. Chem. Soc. Jpn

      Volume: 86, (11) Pages: 1203-1205

    • Peer Reviewed
  • [Journal Article] Sulfur-Containing Pyridylazulenes : Synthesis and Chromogenic Behaviors for Heavy Metal Ions2012

    • Author(s)
      S. Wakabayashi, E. Matsumoto, M. Nishiguchi, R. Yamaoka, M. Ishiura, M. Tsuji, M. Shimizu
    • Journal Title

      Heterocycles

      Volume: 85, (9) Pages: 2251-2258

    • Peer Reviewed
  • [Journal Article] Integrated Reactions Using Addition to Conjugated Imines and Iminium Salts2012

    • Author(s)
      T. Nishi, I. Mizota, M. Shimizu
    • Journal Title

      Pure Appl. Chem

      Volume: 84, (12) Pages: 2609-2617

    • Peer Reviewed
  • [Journal Article] Synthesis of Nitrogen-containing Heterocycles Using Conjugate Addition Reactions of Nucleophiles to α,β-Unsaturated Imines2012

    • Author(s)
      I. Hachiya, I. Mizota, M. Shimizu
    • Journal Title

      Heterocycles

      Volume: 85, (5) Pages: 993-1016

    • Peer Reviewed
  • [Journal Article] Synthesis of γ,δ-Unsaturated Quaternary α-Alkylamino Acids Using Umpolung Reaction and Claisen Rearrangement2012

    • Author(s)
      I. Mizota, K. Tanaka, M. Shimizu
    • Journal Title

      Tetrahedron Lett

      Volume: 53, (14) Pages: 1847-1850

    • Peer Reviewed
  • [Journal Article] Regioselctive Ring-opening Reaction of 2-Mono-substituted Azetidin-3-ones Promoted by the Combined Use of Titanium Tetraiodide and Its Chloro or Bromo Counterpart2012

    • Author(s)
      S. Hata, D. Fukuda, I. Hachiya, M. Shimizu
    • Journal Title

      Heterocycles

      Volume: 84, (1) Pages: 301-307

    • Peer Reviewed
  • [Journal Article] Synthesis of α,α-Disubstituted α-Amino Esters : Nucleophilic Addition to Iminium Salts Generated from Amino Ketene Silyl Acetals2011

    • Author(s)
      S. Hata, H. Koyama, M. Shimizu
    • Journal Title

      J. Org. Chem

      Volume: 76, (23) Pages: 9670-9677

    • Peer Reviewed
  • [Journal Article] Reductive Aminopropylation of Ketene Silyl (Thio)acetals Leading to the Synthesis of δ-Amino Esters2011

    • Author(s)
      I. Mizota, S. Agatani, I. Hachiya, M. Shimizu
    • Journal Title

      Tetrahedron Lett

      Volume: 52, (41) Pages: 5388-5391

    • Peer Reviewed
  • [Journal Article] Double Nucleophilic Addition Reaction to Acrolein with Ketene Silyl Acetals and Allylborolanes Catalyzed by Proline2011

    • Author(s)
      M. Shimizu, M. Kawanishi, A. Itoh, I. Mizota, I. Hachiya
    • Journal Title

      Chem. Lett

      Volume: 40, (8) Pages: 862-863

    • Peer Reviewed
  • [Journal Article] Research Progress of Gel Polymer Electrolytes for Lithium Ion Batteries2011

    • Author(s)
      P. Zhang, L. Li, D. He, Y. Wu, M. Shimizu
    • Journal Title

      Acta Polymerica Sinica

      Volume: 2 Pages: 125-131

    • Peer Reviewed
  • [Journal Article] Titanium Tetraiodide Promoted Reductive Enolate Formation of a-Tosyloxy Ketone Derivatives and Aldol Reaction with Aldehydes2011

    • Author(s)
      I. Hachiya, T. Inagaki, Y. Ishihara, M. Shimizu
    • Journal Title

      Bull. Chem. Soc. Jpn

      Volume: 84, (4) Pages: 419-421

    • Peer Reviewed
  • [Presentation] α-イミノチオエステルに対するタンデムN-アルキル化/Michael2014

    • Author(s)
      付加反応,尹大成, 溝田功, 清水真
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学, 名古屋市
    • Year and Date
      20140327-30
  • [Presentation] β,γ-アルキニル α-イミノエステルに対するN-アルキル化を活用した四級アミノ酸誘導体合成2014

    • Author(s)
      溝田功, 清水真
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学, 名古屋市
    • Year and Date
      20140327-30
  • [Presentation] β,γ-アルケニル-α-イミノエステルに対するタンデムN-アルキル化/ビニロガスアルドール反応2014

    • Author(s)
      田中裕貴, 清水真
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学, 名古屋市
    • Year and Date
      20140327-30
  • [Presentation] 極性転換反応を利用したα-アシロキイミノエステルへのN,N-ジアルキル化反応およびN,N,C-トリアルキル化反応2014

    • Author(s)
      日本化学会第94春季年会
    • Organizer
      前田達也, 清水真
    • Place of Presentation
      名古屋大学, 名古屋市
    • Year and Date
      20140327-30
  • [Presentation] 環状アミノケテンシリルアセタールから調製したイミニウム塩への求核付加反応2013

    • Author(s)
      矢頭篤洋, 清水真
    • Organizer
      第44回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      静岡大学, 浜松市
    • Year and Date
      20131102-03
  • [Presentation] α-イミノエステルに対するC-シリル化に続くアザ-Brook 転位を活用した分子間求核付加反応,片野隆文2013

    • Author(s)
      溝田功, 清水真
    • Organizer
      第44回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      静岡大学, 浜松市
    • Year and Date
      20131102-03
  • [Presentation] 極性転換反応を利用したα-スルホキシイミノエステルへのN,N-ジアルキル化反応およびN,N,C-トリアルキル化反応2013

    • Author(s)
      前田達也, 清水真
    • Organizer
      第44回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      静岡大学, 浜松市
    • Year and Date
      20131102-03
  • [Presentation] Integrated Reactions Based on the Sequential Addition to Conjugated Imines2013

    • Author(s)
      Makoto Shimizu
    • Organizer
      The 23rd International Symposium on Fine Chemistry and Functional Polymers & IUPAC 9th International Conference on Novel Materials and Their Synthesis
    • Place of Presentation
      Shanghai, China
    • Year and Date
      20131017-22
  • [Presentation] Umpoled Tandem Reaction of α-Imino Esters2013

    • Author(s)
      Makoto Shimizu
    • Organizer
      The 15th Asian Chemical Congress (ACC15)
    • Place of Presentation
      Singapore
    • Year and Date
      20130819-23
  • [Presentation] Unsaturated Imino Compounds as Acceptors for Multiple Nucleophiles2013

    • Author(s)
      Makoto Shimizu
    • Organizer
      1st International Symposium on Nature Product, Biotechnology and Catalysis
    • Place of Presentation
      Hohhot, China
    • Year and Date
      20130717-19
  • [Presentation] α-イミノエステルの極性転換/酸化反応を利用するジアステレオ選択的Mannich 反応2013

    • Author(s)
      溝田功, 中島雄司, 清水真
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学, 草津市
    • Year and Date
      20130322-25
  • [Presentation] α-イミノチオエステルに対する極性転換反応を活用した連続的炭素-炭素結合形成反応2013

    • Author(s)
      上田千裕, 溝田功, 清水真
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学,草津市
    • Year and Date
      20130322-25
  • [Presentation] α-イミノアリルエステルへのN-アルキル化に続くClaisen 転位2013

    • Author(s)
      溝田功, 清水真
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学, 草津市
    • Year and Date
      20130322-25
  • [Presentation] 有機反応場の合理的設計と合成反応の高次制御2013

    • Author(s)
      清水真
    • Organizer
      KH ネオケム講演会
    • Place of Presentation
      KHネオケム
    • Year and Date
      2013-06-25
  • [Presentation] 共役イミン誘導体を活用する新規合成反応2013

    • Author(s)
      清水真
    • Organizer
      東京工業大学化学科セミナー
    • Place of Presentation
      東京工業大学, 東京都
    • Year and Date
      2013-06-21
  • [Presentation] 共役イミン誘導体-ハイブリッド合成素子2012

    • Author(s)
      清水真
    • Organizer
      第43回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      名古屋工業大学, 名古屋市
    • Year and Date
      20121110-11
  • [Presentation] Claisen Rearrangement of α-Imino Allyl Ester Using An Umpolung Reaction2012

    • Author(s)
      Isao Mizota, Makoto Shimizu
    • Organizer
      The 22nd International Symposium on Fine Chemistry and Functional Polymers & IUPAC 8th International Conference on Novel Materials and Their Synthesis
    • Place of Presentation
      Xi'An, China
    • Year and Date
      20121014-19
  • [Presentation] α-Imino Esters as Versatile Building Blocks in Organic Synthesis2012

    • Author(s)
      Makoto Shimizu
    • Organizer
      The 22nd International Symposium on Fine Chemistry and Functional Polymers & IUPAC 8th International Conference on Novel Materials and Their Synthesis
    • Place of Presentation
      Xi'An, China
    • Year and Date
      20121014-19
  • [Presentation] イミノマロネートに対するN-アルキル化および酸化反応を活用したタンデム型四級α-アミノ酸誘導体合成2012

    • Author(s)
      武鹿美希, 清水真
    • Organizer
      第29回有機合成化学セミナー
    • Place of Presentation
      静岡コンベンションアーツセンター, 静岡市
    • Year and Date
      20120905-07
  • [Presentation] α-イミノリン酸エステルの極性転換反応を利用する Horner- Wadsworth-Emmons 反応2012

    • Author(s)
      立石雅聖, 清水真
    • Organizer
      第29回有機合成化学セミナー
    • Place of Presentation
      静岡コンベンションアーツセンター, 静岡市
    • Year and Date
      20120905-07
  • [Presentation] α-イミノエステル類の極性転換反応を活用する Claisen 転位反応2012

    • Author(s)
      溝田功, 清水真
    • Organizer
      第29回有機合成化学セミナー
    • Place of Presentation
      静岡コンベンションアーツセンター, 静岡市
    • Year and Date
      20120905-07
  • [Presentation] α-イミノエステルへの N-アルキル化に続く求電子付加反応とフロー合成2012

    • Author(s)
      佐野貴則, 溝田功, 清水真
    • Organizer
      第29回有機合成化学セミナー
    • Place of Presentation
      静岡コンベンションアーツセンター, 静岡市
    • Year and Date
      20120905-07
  • [Presentation] Nucleophilic Addition to Conjugated Imines Leading to the Synthesis of HeterocyclesUmpoled Tandem Reaction of α-Imino Esters2012

    • Author(s)
      Makoto Shimizu
    • Organizer
      4th Congress of the European Association for Chemical and Molecular Sciences
    • Place of Presentation
      Prague, Czech Republic
    • Year and Date
      20120826-30
  • [Presentation] 環状アミノケテンシリルアセタールから調製したイミニウム塩への求核付加反応2012

    • Author(s)
      小山裕, 矢頭篤洋, 清水真
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応義塾大学, 横浜市
    • Year and Date
      20120325-28
  • [Presentation] アミノケテンシリルアセタールから調製したイミニウム塩を活用するα,α-二置換α-アミノエステルの合成2012

    • Author(s)
      小山裕, 波多慎吾, 清水真
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応義塾大学, 横浜市
    • Year and Date
      20120325-28
  • [Presentation] 1,3-Aza-Brook転位を活用したα-イミノエステルの環化反応2012

    • Author(s)
      高尾侑希, 葛山陽菜, 清水真
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応義塾大学, 横浜市
    • Year and Date
      20120325-28
  • [Presentation] 1,2-Aza-Brook転位を活用したα-イミノエステルの分子内環化反応による2,2-二置換インドリン-3-オンの合成と天然物合成への応用2012

    • Author(s)
      高尾侑希, 清水真
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応義塾大学, 横浜市
    • Year and Date
      20120325-28
  • [Presentation] β,γ-アルケニル-α-イミノエステルのN-アルキル化に関する研究2012

    • Author(s)
      上村聡 ,田中裕貴, 清水真
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応義塾大学, 横浜市
    • Year and Date
      20120325-28
  • [Presentation] α-イミノチオエステルに対する極性転換反応を活用した炭素-炭素結合形成反応2012

    • Author(s)
      上田千裕, 溝田功, 清水真
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応義塾大学, 横浜市
    • Year and Date
      20120325-28
  • [Presentation] Integrated Reactions Using Addition to Conjugated Imines2011

    • Author(s)
      Makoto Shimizu
    • Organizer
      The 21st International Symposium on Fine Chemistry and Functional Polymers & IUPAC 7th International Symposium on Novel Materials and Their Synthesis
    • Place of Presentation
      Shanghai, China
    • Year and Date
      20111016-21
  • [Presentation] Nucleophilic Addition to Conjugated Imines Leading to the Synthesis of Heterocycles2011

    • Author(s)
      Makoto Shimizu. Iwao Hachiya, Isao Mizota
    • Organizer
      14th Asian Chemical Congress
    • Place of Presentation
      Bangkok, Thailand
    • Year and Date
      20110905-08
  • [Presentation] エノラート誘導体の酸化によるイミニウム塩の形成及びα-アミノ酸誘導体の効率的合成反応の開発2011

    • Author(s)
      波多慎吾, 小山裕, 清水真
    • Organizer
      第99回有機合成シンポジウム
    • Place of Presentation
      慶応義塾大学, 東京都
    • Year and Date
      20110615-16
  • [Book] In Iodine : Chemistry and Application, T. Kaiho, Ed, John Wiley & Sons: Hoboken, NJ2014

    • Author(s)
      Junji Inanaga, Makoto Shimizu, Iwao Hachiya
    • Publisher
      Samarium(II) Iodide and Titanium(IV) Iodide(in press)
  • [Book] EDOTの効率的な合成法,奥崎 秀典監修, PEDOT の材料物性とデバイス応用2012

    • Author(s)
      清水真, 八谷巌
    • Total Pages
      17-23(405)
    • Publisher
      サイエンス&テクノロジー, 東京
  • [Remarks]

    • URL

      http://www.fine.chem.mie-u.ac.jp/

URL: 

Published: 2015-06-25  

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