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Development of C2-Symmetric Pyridine N-Oxides as New Nucleophilic Catalysts and Application for the Asymmetric Synthesis

Research Project

Project/Area Number 23655045
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Organic chemistry
Research InstitutionTokyo University of Science

Principal Investigator

SHIINA Isamu  東京理科大学, 理学部, 教授 (40246690)

Project Period (FY) 2011 – 2013
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2013: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2012: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2011: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords有機化学 / 有機合成化学 / 不斉触媒 / 求核性塩基触媒 / 不斉合成 / 光学分割 / 求核性塩基 / 軸不斉 / 不斉配位子
Research Abstract

We had found an effective coupling reaction of carboxylic acids and alcohols using aromatic anhydrides by the promotion of nucleophilic base catalysts, such as DMAP and DMAPO. Furthermore, we have developed a method for the preparation of optically active carboxylic esters by the kinetic resolution of racemic secondly alcohols using carboxylic anhydrides, and achiral carboxylic acids via mixed-anhydride formation method in the presence of chiral acyl-transfer catalysts. In this study, we succeeded in preparing new pyridine oxide compounds (DM-DMAPO and DM-DMQO) and other nucleophilic base catalysts. Moreover, the following reactions were performed in the presence of any of these as a catalyst, (1) a process for producing an ester or amide compound from a carboxylic acid equivalent and an alcohol or amine, (2) an asymmetric esterification reaction, and (3) an asymmetric aldol and allylation reactions.

Report

(4 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Research-status Report
  • 2011 Research-status Report
  • Research Products

    (54 results)

All 2014 2013 2012 2011 Other

All Journal Article (20 results) (of which Peer Reviewed: 19 results) Presentation (29 results) (of which Invited: 4 results) Book (4 results) Remarks (1 results)

  • [Journal Article] Asymmetric Mukaiyama Aldol Reactions Using Chiral Diamine-Coordinated Sn(II) Triflate: Development and Application to Natural Product Synthesis2014

    • Author(s)
      I. Shiina
    • Journal Title

      The Chemical Record

      Volume: 14 Issue: 1 Pages: 144-183

    • DOI

      10.1002/tcr.201300022

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 脱水縮合を伴う速度論的光学分割反応の開発2014

    • Author(s)
      中田健也、椎名 勇
    • Journal Title

      有機合成化学協会誌

      Volume: 72

    • NAID

      130004691492

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of Racemic 2-Hydroxy-・-butyrolactones by Asymmetric Esterification Using Diphenylacetic Acid with Pivalic Anhydride and a Chiral Acyl-Transfer Catalyst2013

    • Author(s)
      Kenya Nakata, Kouya Gotoh, Keisuke Ono, Kengo Futami, Isamu Shiina
    • Journal Title

      Organic Letters

      Volume: 15 Pages: 1170-1173

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of Racemic α-Hydroxyphosphonates by Asymmetric Esterification Using Achiral Carboxylic Acids with Pivalic Anhydride and a Chiral Acyl-Transfer Catalyst2013

    • Author(s)
      Isamu Shiina, Keisuke Ono, Takayoshi Nakahara
    • Journal Title

      Chemical Communications

      Volume: 49 Pages: 10700-10702

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] An Enantiodivergent Synthesis of (+)- and (-)-Centrolobines via the Asymmetric Esterification Catalyzed by (R)-(+)-N-Methylbenzoguanidine ((R)-NMBG)2013

    • Author(s)
      Kenya Nakata, Tatsuya Tokumaru, Hidetoshi Iwamoto, Yutaka Nishigaichi, Isamu Shiina
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 2 Pages: 920-922

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Total synthesis of AMF-26, an antitumor agent for inhibition of the Golgi system, targeting ADP-ribosylation factor 12013

    • Author(s)
      Shiina I, Umezaki Y, Ohashi Y, Yamazaki Y, Dan S, Yamori T
    • Journal Title

      J Med Chem

      Volume: 56(1) Issue: 1 Pages: 150-159

    • DOI

      10.1021/jm301695c

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of Racemic 2-Hydroxy-γ-butyrolactones by Asymmetric Esterification Using Diphenylacetic Acid with Pivalic Anhydride and a Chiral Acyl-Transfer Catalyst2013

    • Author(s)
      K. Nakata, K. Gotoh, K. Ono, K. Futami, I. Shiina
    • Journal Title

      Organic Letters

      Volume: 15 Issue: 6 Pages: 1170-1173

    • DOI

      10.1021/ol303453j

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Fine Structures in Vibrational Circular Dichroism Spectra of Chiral Molecules with Rotatable Hydroxyl Groups and Their Application in the Analysis of Local Intermolecular Interactions2013

    • Author(s)
      K. Konno, I. Shiina, H. Yui
    • Journal Title

      Journal of Molecular Structure

      Volume: 1035 Pages: 260-266

    • DOI

      10.1016/j.molstruc.2012.11.025

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Benzylic Alcohols by the Enantioselective Esterification Using 3-PCA with Chiral Acyl-transfer Catalysts2012

    • Author(s)
      Isamu Shiina, Kenya Nakata, Keisuke Ono, Teruaki Mukaiyama
    • Journal Title

      Helvetica Chimica Acta

      Volume: 95 Pages: 1891-1911

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] A New Method for Production of Chiral 2-Aryloxypropanoic Acids Using Effective Kinetic Resolution of Racemic 2-Aryloxycarboxylic Acids2012

    • Author(s)
      A. Tengeiji, K. Nakata, K. Ono, I. Shiina
    • Journal Title

      Heterocycles

      Volume: 86 Issue: 2 Pages: 1227-1252

    • DOI

      10.3987/com-12-s(n)79

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of Racemic Secondary Benzylic Alcohols by the Enantioselective Esterification Using 3-PCA with Chiral Acyl-transfer Catalysts2012

    • Author(s)
      I. Shiina, K. Nakata, K. Ono, T. Mukaiyama
    • Journal Title

      Helvetica Chimica Acta

      Volume: 95 Issue: 10 Pages: 1891-1911

    • DOI

      10.1002/hlca.201200434

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] A New Method for Production of Chiral 2-Aryl-2-fluorpropanoic Acids Using an Effective Kinetic Resolution of Racemic 2-Aryl-2-fluoropropanic Acids2012

    • Author(s)
      A. Tengeiji, I. Shiina
    • Journal Title

      Molecules

      Volume: 17 Issue: 6 Pages: 7356-7378

    • DOI

      10.3390/molecules17067356

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of the Racemic 1-(Aryloxazol-2-yl)carbinols with Achiral Carboxylic Acids by Asymmetric Esterification : A New Method for the Preparation of Chiral 1, 2-Amino Alcohols2011

    • Author(s)
      Kenya Nakata, Keisuke Ono, Isamu Shiina
    • Journal Title

      Heterocycles

      Volume: 82 Pages: 1171-1180

    • NAID

      40018702708

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] (R)-(+)-N-Methylbenzoguanidine ((R)-NMBG) Catalyzed Kinetic Resolution of Racemic Secondary Benzylic Alcohols with Free Carboxylic Acids by Asymmetric Esterification2011

    • Author(s)
      Kenya Nakata, Isamu Shiina
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 9 Pages: 7092-7096

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] A Convenient Method for the Kinetic Resolution of Racemic 2-Hydroxyalkanoates Using Diphenylacetic Anhydride (DPHAA) and Chiral Acyl-transfer Catalyst2011

    • Author(s)
      Kenya Nakata, Akihiro Sekiguchi, Isamu Shiina
    • Journal Title

      Tetrahedron : Asymmetry

      Volume: 22 Pages: 1610-1619

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] (R)-(+)-N-Methylbenzoguanidine ((R)-NMBG) Catalyzed Kinetic Resolution of Racemic Secondary Benzylic Alcohols with Free Carboxylic Acids by Asymmetric Esterification2011

    • Author(s)
      Nakata, K.; Shiina, I.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 9 Pages: 7092-7096

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Convenient Method for the Kinetic Resolution of Racemic 2-Hydroxyalkanoates Using Diphenylacetic Anhydride (DPHAA) and a Chiral Acyl-Transfer Catalyst2011

    • Author(s)
      Nakata, K.; Sekiguchi, A.; Shiina, I.
    • Journal Title

      Tetrahedron: Asymmetry

      Volume: 22 Pages: 1610-1619

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of the Racemic 1-Heteroarylcarbinols by the Asymmetric Esterification Using Diphenylacetic Acid with Pivalic Anhydride and a Chiral Acyl-Transfer Catalyst2011

    • Author(s)
      Shiina, I.; Ono, K.; Nakata, K.
    • Journal Title

      Chem. Lett.

      Volume: 40 Pages: 147-149

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Kinetic Resolution of the Racemic 1-(Aryloxazol-2-yl)carbinols with Achiral Carboxylic Acids by Asymmetric Esterification: A New Method for the Preparation of Chiral 1,2-Amino Alcohols2011

    • Author(s)
      Nakata, K.; Ono, K.; Shiina, I.
    • Journal Title

      Heterocycles

      Volume: 82 Pages: 1171-1180

    • NAID

      40018702708

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Various Synthetic Method Using Aromatic Carboxylic Anhydrides2011

    • Author(s)
      Shiina, I.
    • Journal Title

      TCI MAIL

      Volume: 144 Pages: 2-15

    • Related Report
      2011 Research-status Report
  • [Presentation] ラセミアミノ酸保護体の動的速度論光学分割による光学活性アミノ酸の合成2014

    • Author(s)
      天花寺厚・中原貴佳・椎名勇
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Year and Date
      2014-03-27
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ2-ヒドロキシケトンおよびその等価体の速度論光学分割2014

    • Author(s)
      張キ・中原貴佳・石川 凌・中田健也・椎名勇
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Year and Date
      2014-03-27
    • Related Report
      2013 Final Research Report
  • [Presentation] 計算化学によるトランスアシル化触媒(反応)の機能評価-抗肥満剤の合成を例として, 有機分子触媒による未来型分子変換2013

    • Author(s)
      椎名勇
    • Organizer
      第2回有機分子触媒
    • Place of Presentation
      ラフォーレ倶楽部 伊東温泉 湯の庭
    • Year and Date
      2013-09-14
    • Related Report
      2013 Final Research Report
  • [Presentation] Non-Enzymatic Dynamic Kinetic Resolution of Racemic 2-Arylalkanoic Acids Using Chiral Acyl-Transfer Catalysts2013

    • Author(s)
      Isamu Shiina
    • Organizer
      International Symposium on Homogeneous Chemical Reactivity
    • Place of Presentation
      Ibaraki University
    • Year and Date
      2013-06-14
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] ラセミ-2-ヒドロキシオキシムおよびその等価体の速度論的光学分割2013

    • Author(s)
      中田健也・二見賢吾・張 キ・中原貴佳・小野圭輔・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-25
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ-2-ヒドロキシリン酸エステル類の速度論的光学分割2013

    • Author(s)
      小野圭輔・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-25
    • Related Report
      2013 Final Research Report
  • [Presentation] 高選択的な脱水縮合反応の開発ならびに薬理活性化合物の不斉合成研究2013

    • Author(s)
      椎名勇
    • Organizer
      日本化学会第93春季年会平成24年度日本化学会学術賞
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-24
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ-2-アリールプロピオン酸類の動的速度論光学分割の反応メカニズム解析2013

    • Author(s)
      小野圭輔・天花寺 厚・中田健也・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-24
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ-2-アリール-2-フルオロプロピオン酸類の速度論的光学分割2013

    • Author(s)
      天花寺 厚・小野圭輔・中田健也・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-24
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ-2-アミノ-2-アリール酢酸類の静的および動的速度論光学分割反応の開発2013

    • Author(s)
      中田健也・川西達也・小野圭輔・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-24
    • Related Report
      2013 Final Research Report
  • [Presentation] 環状ラセミ-2-ヒドロキシカルボン酸誘導体の速度論的光学分割2013

    • Author(s)
      中田健也・北島寛能・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-24
    • Related Report
      2013 Final Research Report
  • [Presentation] ニコチン酸無水物を用いたラセミ第2級アルコールの速度論的光学分割法の開発2013

    • Author(s)
      中田健也・小野圭輔・椎名勇
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-24
    • Related Report
      2013 Final Research Report
  • [Presentation] 不斉エステル化反応によるラセミ-2-アリールプロピオン酸類の動的速度論光学分割法の開発2012

    • Author(s)
      小野圭輔・中田健也・椎名勇
    • Organizer
      第102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
      2012-11-09
    • Related Report
      2013 Final Research Report
  • [Presentation] Non-Enzymatic Dynamic Kinetic Resolution of Racemic α-Arylalkanoic Acids2012

    • Author(s)
      Isamu Shiina
    • Organizer
      11th Symposium on Chemical Approaches to Chirality
    • Place of Presentation
      Tokyo University of Science
    • Year and Date
      2012-09-26
    • Related Report
      2013 Final Research Report
  • [Presentation] A New Method for Production of Chiral 2-Aryloxypropanoic Acids Using Effective Kinetic Resolution of Racemic 2-Aryloxycarboxylic Acids2012

    • Author(s)
      Atsushi Tengeiji, Kenya Nakata, Keisuke Ono, Isamu Shiina
    • Organizer
      11th Symposium on Chemical Approaches to Chirality
    • Place of Presentation
      Tokyo University of Science
    • Year and Date
      2012-09-26
    • Related Report
      2013 Final Research Report
  • [Presentation] 触媒的不斉縮合反応 - 計算科学による活性化剤の設計と展開2012

    • Author(s)
      椎名勇
    • Organizer
      日本化学会関東支部講演会「進化する有機分子触媒-その最先端と展望-
    • Place of Presentation
      日本化学会7階ホール
    • Year and Date
      2012-08-31
    • Related Report
      2013 Final Research Report
  • [Presentation] Dynamic Kinetic Resolution of 2-Arylpropanoic Acids via the Asymmetric Esterification2012

    • Author(s)
      Keisuke Ono, Kenya Nakata, Isamu Shiina
    • Organizer
      244th American Chemical Society National Meeting
    • Place of Presentation
      Pennsylvania Convention Center, Philadelphia, PA
    • Year and Date
      2012-08-19
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ- 2-アリールプロピオン酸類の立体反転を伴う動的な速度論的光学分割法の開発2012

    • Author(s)
      小野圭輔・中田健也・椎名勇
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉キャンパス
    • Year and Date
      2012-03-26
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ-2-アリールオキシプロピオン酸類の速度論的光学分割2012

    • Author(s)
      天花寺 厚・中田健也・小野圭輔・椎名勇
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉キャンパス
    • Year and Date
      2012-03-26
    • Related Report
      2013 Final Research Report
  • [Presentation] リダイフェン合成展開による創薬戦略2012

    • Author(s)
      椎名 勇
    • Organizer
      文部科学省がん支援・化学療法基盤支援活動 第2回シンポジウム(招待講演)
    • Place of Presentation
      慶応大学日吉キャンパス
    • Related Report
      2011 Research-status Report
  • [Presentation] ゴルジ体阻害活性を有する新奇双環性化合物の不斉全合成2012

    • Author(s)
      椎名 勇
    • Organizer
      「Cancer Cell Informaticsによる創薬研究会」第2回研究会(招待講演)
    • Place of Presentation
      公益財団法人がん研究会
    • Related Report
      2011 Research-status Report
  • [Presentation] ラセミ2-アリールプロピオン酸類の静的および動的速度論分割反応の開発2011

    • Author(s)
      椎名勇
    • Organizer
      第4回有機触媒シンポジウム
    • Place of Presentation
      東京理科大学神楽坂キャンパス
    • Year and Date
      2011-09-17
    • Related Report
      2013 Final Research Report
  • [Presentation] 不斉エステル化反応によるラセミ2-アリールプロピオン酸類の速度論的光学分割2011

    • Author(s)
      小野圭輔・中田健也・椎名勇
    • Organizer
      第99回有機合成シンポジウム
    • Place of Presentation
      慶応義塾大学薬学部
    • Year and Date
      2011-06-15
    • Related Report
      2013 Final Research Report
  • [Presentation] 人工不斉触媒を用いた静的および動的速度論分割反応の開発2011

    • Author(s)
      椎名勇
    • Organizer
      埼玉大学大学院理工学研究科講演会
    • Place of Presentation
      埼玉大学工学部
    • Year and Date
      2011-06-13
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ2-アリールプロピオン酸類の静的および動的速度論分割反応の開発2011

    • Author(s)
      椎名 勇
    • Organizer
      第4回有機触媒シンポジウム(招待講演)
    • Place of Presentation
      東京理科大学
    • Related Report
      2011 Research-status Report
  • [Presentation] 計算化学によるトランスアシル化触媒(反応)の機能評価-抗肥満剤の合成を例として

    • Author(s)
      椎名 勇
    • Organizer
      有機分子触媒による未来型分子変換 第2回有機分子触媒 若手セミナー招待講演
    • Place of Presentation
      ラフォーレ倶楽部 伊東温泉 湯の庭
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 抗腫瘍活性化合物リダイフェン-合成・創薬展開からメカニズム解析まで

    • Author(s)
      椎名 勇
    • Organizer
      BioJapan 2013 World Business Forum
    • Place of Presentation
      パシフィコ横浜
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 高選択的な脱水縮合反応の開発ならびに薬理活性化合物の不斉合成研究

    • Author(s)
      椎名 勇
    • Organizer
      平成24年度「日本化学会(第30回)学術賞」受賞講演
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] 触媒的不斉縮合反応 - 計算科学による活性化剤の設計と展開

    • Author(s)
      椎名 勇
    • Organizer
      日本化学会関東支部講演会「進化する有機分子触媒-その最先端と展望-」
    • Place of Presentation
      日本化学会7階ホール
    • Related Report
      2012 Research-status Report
    • Invited
  • [Book] Natural Lactones and Lactams: Synthesis, Occurrence and Biological Activity2013

    • Author(s)
      Isamu Shiina, Kenya Nakata
    • Total Pages
      376
    • Publisher
      Wiley-VCH Verlag GmbH & Co. KGaA
    • Related Report
      2013 Annual Research Report
  • [Book] トップドラッグから学ぶ創薬化学2012

    • Author(s)
      椎名 勇
    • Total Pages
      199
    • Publisher
      東京化学同人
    • Related Report
      2011 Research-status Report
  • [Book] Various Synthetic Methods Using Aromatic Carboxylic Anhydrides2011

    • Author(s)
      Isamu Shiina
    • Publisher
      TCI MAIL Int. Ed
    • Related Report
      2013 Final Research Report
  • [Book] 天然物合成で活躍した反応2011

    • Author(s)
      椎名 勇
    • Total Pages
      209
    • Publisher
      化学同人
    • Related Report
      2011 Research-status Report
  • [Remarks] 研究者情報ホームページ

    • URL

      http://www.tus.ac.jp/fac_grad/p/index.php?A06637

    • Related Report
      2013 Final Research Report

URL: 

Published: 2011-08-05   Modified: 2019-07-29  

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