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Allylic and propargylic substitutions using the picolinoxy leaving group and application to organic synthesis

Research Project

Project/Area Number 23550119
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

KOBAYASHI Yuichi  東京工業大学, 生命理工学研究科, 教授 (90153650)

Project Period (FY) 2011 – 2013
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2013: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2011: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywordsアリル化反応 / 銅試薬 / アセチレン銅試薬 / ピコリン酸アリルエステル / リン酸アリルエステル / 第4級炭素構築 / シクロバクチオール / ジャスモン酸 / ピコリン酸アリル / ピコリン酸プロパルギル / 2,6-ジ置換シクロヘキサノン / アリルピコレート / ピコリン酸脱離基 / 光学活性 / アナストレフィン / プロパルギルエステル / 芳香族Grignard試薬 / プロスタグランジン
Research Abstract

Allylic substitution of secondary allylic picolinates with copper reagents were investigated to establish methods for: (1) construction of quaternary carbon center; (2) synthesis of anti inflammatory cyclobakuchiols; (3) synthesis of trans 2,6-disubstituted cyclohexanones; (4) introduction of acetylene on a cyclopentane ring; (5) Pd-catalyzed allylic substitution of 1,3-disubstituted secondary allylic esters with ketone enolates.

Report

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

    (41 results)

All 2014 2013 2012 2011 Other

All Journal Article (15 results) (of which Peer Reviewed: 14 results) Presentation (25 results) Remarks (1 results)

  • [Journal Article] Allylic substitution of esters derived from 2-bromocyclohex-2-enol with aryl copper reagents and synthetic utilization of the derived anti SN2 products2014

    • Author(s)
      Atsushi Ikoma and Yuichi Kobayashi
    • Journal Title

      Synlett

      Volume: 25 Issue: 08 Pages: 1150-1154

    • DOI

      10.1055/s-0033-1341065

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of trans-2,6-Disubstituted Cyclohexanones through Allylic Substitution2014

    • Author(s)
      Yuichi Kobayashi, Chao Feng, Atsushi Ikoma, Narihito Ogawa, and Takayuki Hirotsu
    • Journal Title

      Org. Lett.

      Volume: 16 Issue: 3 Pages: 760-763

    • DOI

      10.1021/ol403472y

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of cyclobakuchiols A, B, and C using conformation-controlled stereoselective reactions2014

    • Author(s)
      Kawashima, H. ; Kaneko, Y. ; Sakai, M. ; Kobayashi, Y
    • Journal Title

      Chem. Eur. J

      Volume: 20 Issue: 1 Pages: 272-278

    • DOI

      10.1002/chem.201303538

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Installation of a chiral side chain to a 2-alkylidene-1-cycloalkan-1-ol unit by using allylic substitution2013

    • Author(s)
      Feng, C. ; Kobayashi, Y
    • Journal Title

      Eur. J. Org. Chem

      Volume: 2013 Issue: 29 Pages: 6666-6676

    • DOI

      10.1002/ejoc.201300792

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Reinvestigation of palladium-catalyzed allylation of the monoacetate of 4-cyclopentene-1, 3-diol and synthesis of the coronafacic acid ethyl ester2013

    • Author(s)
      Kinouchi, W. ; Kosaki, Y. ; Kobayashi, Y
    • Journal Title

      Tetrahedron Lett

      Volume: 54 Issue: 51 Pages: 7017-7020

    • DOI

      10.1016/j.tetlet.2013.10.052

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Construction of quaternary carbon centers by using substitution of γ,γ-disubstituted secondary allylic picolinates with alkylcopper reagents2013

    • Author(s)
      Chao Feng, Yuki Kaneko, Yuichi Kobayashi
    • Journal Title

      Tetrahedron Lett.

      Volume: 54 Issue: 35 Pages: 4629-4632

    • DOI

      10.1016/j.tetlet.2013.06.046

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Allylic Substitution for Construction of a Chiral Quaternary Carbon Possessing an Aryl Group2013

    • Author(s)
      Chao Feng and Yuichi Kobayashi
    • Journal Title

      J. Org. Chem.

      Volume: 78 Issue: 8 Pages: 3755-3766

    • DOI

      10.1021/jo400248y

    • Related Report
      2013 Annual Research Report 2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of the amino acid conjugates of epi-jasmonic acid2012

    • Author(s)
      N.Ogawa, Y.Kobayashi
    • Journal Title

      Amino Acids

      Volume: 42 Issue: 5 Pages: 1955-1966

    • DOI

      10.1007/s00726-011-0925-z

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Efficient synthesis of substituted quinolines through intramoluecular addition of aryl anion to carbonyl carbon2012

    • Author(s)
      Kobayashi, Y. ; Igarashi, J. ; Feng, C. ; Tojo, T
    • Journal Title

      Tetrahedron Lett

      Volume: 53 Issue: 29 Pages: 3742-3745

    • DOI

      10.1016/j.tetlet.2012.05.003

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Development of New Methods for Synthesis of Cyclopentanoids Using the Monoacetate of Cyclopent-4-ene-1,3-diol2011

    • Author(s)
      小林雄一
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 69 Issue: 6 Pages: 680-690

    • DOI

      10.5059/yukigoseikyokaishi.69.680

    • NAID

      10028294026

    • ISSN
      0037-9980, 1883-6526
    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of an Advanced Intermediate toward the hNK-1 Antagonist with the Cyclopentane Core2011

    • Author(s)
      K.Nakata, Y.Kiyotsuka, T.Kitazume, Y.Kobayashi
    • Journal Title

      Synlett

      Volume: 2011 Issue: 19 Pages: 2872-2874

    • DOI

      10.1055/s-0031-1289863

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Allylic substitution on cyclopentene and -hexene rings with alkynylcopper reagents2011

    • Author(s)
      Q. Wang. ; Kobayashi, Y
    • Journal Title

      Org. Lett

      Volume: 13 Issue: 02 Pages: 6252-6255

    • DOI

      10.1055/s-0031-1290006

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Allylic Substitution on Cyclopentene and -hexene rings with Alkynylcopper Reagents2011

    • Author(s)
      Q. Wang, Y. Kobayashi
    • Journal Title

      Organic Letters

      Volume: 13 Pages: 6252-6255

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of an Advanced Intermediate toward the hNK-1 Antagonist with the Cyclopentane Core2011

    • Author(s)
      K. Nakata, Y. Kiyotsuka, T. Kitazume, Y. Kobayashi
    • Journal Title

      Synlett

      Volume: no Pages: 2872-2874

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] シクロペンタ-4-エン-1,3-ジオールのモノエステルを活用したシクロペンタノイド合成法の開発と応用2011

    • Author(s)
      小林雄一
    • Journal Title

      有合化

      Volume: 69 Pages: 680-690

    • NAID

      10028294026

    • Related Report
      2011 Research-status Report
  • [Presentation] 有機リチウム試薬由来の銅試薬を用いるアリル化反応による四級炭素の構築2014

    • Author(s)
      尾崎拓里, 小林雄一
    • Organizer
      日化第94春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Final Research Report
  • [Presentation] 有機リチウム試薬由来の銅試薬を用いるアリル化反応による四級炭素の構築2014

    • Author(s)
      尾崎拓里・小林雄一
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Annual Research Report
  • [Presentation] 立体配座制御型アリル化反応を用いるCyclobakuchiol 類の合成2013

    • Author(s)
      川島英久, 酒井将宏, 小林雄一
    • Organizer
      日化第93春季年会
    • Place of Presentation
      立命館大学
    • Year and Date
      2013-03-25
    • Related Report
      2013 Final Research Report
  • [Presentation] S_N2' 型アリル化反応を用いたアナストレフィンの合成研究2013

    • Author(s)
      酒井将宏, 小川熟人, 小林雄一
    • Organizer
      日化第93春季年会
    • Place of Presentation
      立命館大学
    • Year and Date
      2013-03-23
    • Related Report
      2013 Final Research Report
  • [Presentation] アリル化反応を用いた光学活性な四級炭素の構築2013

    • Author(s)
      馮超, 小林雄一
    • Organizer
      日化第93春季年会
    • Place of Presentation
      立命館大学
    • Year and Date
      2013-03-23
    • Related Report
      2013 Final Research Report
  • [Presentation] Pd 触媒を用いたアリル化合物とケトンエノレートの位置および立体選択的反応2013

    • Author(s)
      木野内渉, 小林雄一
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学
    • Year and Date
      2013-03-22
    • Related Report
      2013 Final Research Report
  • [Presentation] コンフォメーション制御による不斉四級炭素構築法を基盤とするCyclobakuchiol類の合成2013

    • Author(s)
      川島英久, 金子悠希, 酒井将宏, 小林雄一
    • Organizer
      第104回有機合成化学シンポジウム
    • Place of Presentation
      早稲田大学国際会議場
    • Related Report
      2013 Final Research Report
  • [Presentation] Total synthesis of cyclobakuchiols by conformation-controlled allylic substitution and michael addition2013

    • Author(s)
      Kawashima, H. ; Sakai, M. ; Kaneko, Y. ; Kobayashi, Y
    • Organizer
      10th International Symposium on Carbanion Chemistry
    • Place of Presentation
      Kyoto, Japan (同志社大学)
    • Related Report
      2013 Final Research Report
  • [Presentation] Total Synthesis of Cyclobakuchiols by Conformation-controlled Allylic Substitution and Michael Addition2013

    • Author(s)
      Hidehisa Kawashima, Masahiro Sakai, Yuki Kaneko, and Yuichi Kobayashi
    • Organizer
      10th International Symposium on Carbanion Chemistry
    • Place of Presentation
      同志社大学
    • Related Report
      2013 Annual Research Report
  • [Presentation] コンフォメーション制御による不斉四級炭素構築法を基盤とするCyclobakuchiol類の合成2013

    • Author(s)
      川島英久・金子悠希・酒井将宏・小林雄一
    • Organizer
      有機合成シンポジウム
    • Place of Presentation
      早稲田大学国際会議場
    • Related Report
      2013 Annual Research Report
  • [Presentation] S_N2' 型アリル化反応を用いたシクロバクチオールAの合成研究2012

    • Author(s)
      酒井将宏, 小林雄一
    • Organizer
      日化第92春季年会
    • Place of Presentation
      慶應大学
    • Year and Date
      2012-03-28
    • Related Report
      2013 Final Research Report
  • [Presentation] α 位選択的プロパギル置換反応を利用したHeliannuol Eの合成研究2012

    • Author(s)
      金子未咲, 小林雄一
    • Organizer
      日化第92春季年会
    • Place of Presentation
      慶應大学
    • Year and Date
      2012-03-28
    • Related Report
      2013 Final Research Report
  • [Presentation] 環状構造を含む基質に対するアリル化反応の位置並びに立体選択性2012

    • Author(s)
      馮超, 小林雄一
    • Organizer
      日化第92春季年会
    • Place of Presentation
      慶應大学
    • Year and Date
      2012-03-28
    • Related Report
      2013 Final Research Report
  • [Presentation] Pd 触媒を用いたシス-4-シクロペンテン-1, 3-ジオールモノアセテートとβ-ケトエステルの反応ならびにその応用2012

    • Author(s)
      木野内渉, 東條敏史, 小林雄一
    • Organizer
      日化第92春季年会
    • Place of Presentation
      慶應大学
    • Year and Date
      2012-03-27
    • Related Report
      2013 Final Research Report
  • [Presentation] ピコリン酸2-ブロモ-2-シクロへキセニルのS_N2'反応を利用したクルクジオールの合成研究2012

    • Author(s)
      生駒篤, 小林雄一
    • Organizer
      日化第92春季年会
    • Place of Presentation
      慶應大学
    • Year and Date
      2012-03-25
    • Related Report
      2013 Final Research Report
  • [Presentation] Stereocontrolled synthesis of epi-jasmonoids, quinine alkaloids, and related compounds2012

    • Author(s)
      Kobayashi, Y
    • Organizer
      BIT's 3rd Annual World Congress of Catal. Asymmet. Synth. ; Session 800, Toward Highly Optically Pure Chemical Materials
    • Place of Presentation
      Beijing International Convention Center, China
    • Related Report
      2013 Final Research Report
  • [Presentation] ピコリン酸2-ブロモ-2-シクロへキセニルのSN2’反応を利用したクルクジオールの合成研究2012

    • Author(s)
      生駒篤・小林雄一
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應大日吉キャンパス
    • Related Report
      2011 Research-status Report
  • [Presentation] Pd 触媒を用いたシス-4-シクロペンテン-1,3-ジオールモノアセテートとβ-ケトエステルの反応ならびにその応用2012

    • Author(s)
      木野内渉・東條敏史・小林雄一
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應大日吉キャンパス
    • Related Report
      2011 Research-status Report
  • [Presentation] 環状構造を含む基質に対するアリル化反応の位置並びに立体選択性2012

    • Author(s)
      馮超・小林雄一
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應大日吉キャンパス
    • Related Report
      2011 Research-status Report
  • [Presentation] α位選択的プロパギル置換反応を利用したHeliannuol Eの合成研究2012

    • Author(s)
      金子未咲・小林 雄一
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應大日吉キャンパス
    • Related Report
      2011 Research-status Report
  • [Presentation] SN2'型アリル化反応を用いたシクロバクチオールAの合成研究2012

    • Author(s)
      酒井将宏・小林雄一
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應大日吉キャンパス
    • Related Report
      2011 Research-status Report
  • [Presentation] Pd触媒を用いたアリル化合物とケトンエノレートの位置および立体選択的反応

    • Author(s)
      木野内渉,小林雄一
    • 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(滋賀県)
    • Related Report
      2012 Research-status Report
  • [Presentation] アリル化反応を用いた光学活性な四級炭素の構築

    • Author(s)
      馮超,小林雄一
    • 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(滋賀県)
    • Related Report
      2012 Research-status Report
  • [Presentation] SN2' 型アリル化反応を用いたアナストレフィンの合成研究

    • Author(s)
      酒井将宏,小川熟人,小林雄一
    • 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(滋賀県)
    • Related Report
      2012 Research-status Report
  • [Presentation] 立体配座制御型アリル化反応を用いるCyclobakuchiol類の合成

    • Author(s)
      川島英久,酒井将宏,小林雄一
    • 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(滋賀県)
    • Related Report
      2012 Research-status Report
  • [Remarks]

    • URL

      http://www.kobayashi.bio.titech.ac.jp

    • Related Report
      2013 Final Research Report

URL: 

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

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