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New Synthetic Methods for the Construction of Organic Molecules Based on the Chemistry of Magnesium Carbenoids

Research Project

Project/Area Number 22590021
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTokyo University of Science

Principal Investigator

SATOH Tsuyoshi  東京理科大学, 理学部, 教授 (20089329)

Project Period (FY) 2010 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2012: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2010: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywordsカルベン / カルベノイド / マグネシウムカルベノイド / 有機マグネシウム / スルホキシド / 有機合成 / 不斉合成 / スルホキシド‐マグネシウム交換反応 / 1,5-CH挿入反応 / 挿入反応 / 有機合成化学
Research Abstract

Carbenes and carbenoids have been known to be highly reactive carbon species that show a variety of unique reactivities. However, those reactive species are not fully used in organic synthesis. In order to solve the problem mentioned above, we used aryl α-haloalkyl (or alkenyl) sulfoxides as the precursors and used sulfoxide-magnesium exchange reaction for generation of much mild magnesium carbenoids (alkylmagnesium carbenoids, magnesium alkylidenecarbenoids, cyclopropylmagnesium carbenoids and cyclobutylmagnesium carbenoids). From the investigation of their nature and reactivity, a variety of novel new synthetic reactions were found and established. In addition, it was established that the method for a synthesis of aryl α-chloroalkyl sulfoxides in optically active form. New asymmetric synthesis of organic molecules was successfullyobtained by using these optically active α-chloroalkyl sulfoxides.

Report

(4 results)
  • 2012 Annual Research Report   Final Research Report ( PDF )
  • 2011 Annual Research Report
  • 2010 Annual Research Report
  • Research Products

    (35 results)

All 2013 2012 2011 2010 Other

All Journal Article (19 results) (of which Peer Reviewed: 19 results) Presentation (15 results) Remarks (1 results)

  • [Journal Article] Efficient Synthesis of Cyclopropanecarboxylic Acids Starting From the Conjugate Addition of Lithium Ester Enolate of 1-Chlorovinyl p-Tolyl Sulfoxides2013

    • Author(s)
      T. Kimura, Y. Hattori, H. Momochi, N. Nakaya, T. Satoh
    • Journal Title

      Synlett

      Volume: 24 Pages: 483-486

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] "Synthesis of Small Ring-containing Conjugated Dienes via the Coupling Reaction of Cyclopropyl- and Cyclobutylmagnesium Carbenoids with α-Sulfonylallyllithoums2013

    • Author(s)
      T. Kimura, M. Inumaru, T. Migimatsu, M. Ishigaki, T. Satoh
    • Journal Title

      Tetrahedron

      Volume: 69 Pages: 3961-3970

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Recent Advances in the Chemistry and Synthetic Uses of Magnesium Carbenoids2012

    • Author(s)
      T. Satoh
    • Journal Title

      Heterocycles

      Volume: 85 Pages: 1-33

    • NAID

      40019137595

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] A New Approach to the Synthesis of 1-Oxaspiro[4.n]alkanes and Tetrahydro- furans by the 1,5-CH Insertion of Magnesium Carbenoids2012

    • Author(s)
      T. Satoh, T. Yasoshima, H. Momochi
    • Journal Title

      Tetrahedron Lett

      Volume: 53 Pages: 2074-2074

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Quantum Chemical Characterization of Magnesium Carbenoids2012

    • Author(s)
      T. Kimura, T. Satoh
    • Journal Title

      J. Organometal. Chem.

      Volume: 715 Pages: 1-4

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Coupling Reaction of Magnesium Alkylidene Carbenoids with α-Sulfonylallyllithiums: An Efficient Route to Multi-Substituted Vinylallenes2012

    • Author(s)
      T. Kimura, G. Kobayashi, M. Ishigaki, M. Inumaru, J. Sakurada, T. Satoh
    • Journal Title

      Synthesis

      Volume: 44 Pages: 3623-3632

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis including asymmetric synthesis of 3-oxabicyclo[3.1.0]hexanes and bicyclo[3.1.0]hexanes by the 1,5-CH insertion reaction of cyclopropylmagnesium carbenoids as the key reaction2012

    • Author(s)
      Tsuyoshi Satoh
    • Journal Title

      Tetrahedron

      Volume: 68 Issue: 4 Pages: 1071-1084

    • DOI

      10.1016/j.tet.2011.11.085

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] New synthesis of multisubstituted cycnocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC inssertion reacation of magnesium carbenoids as the key reaction2012

    • Author(s)
      Hideki Saitoh
    • Journal Title

      Tetrahedron

      Volume: 68 Issue: 11 Pages: 2481-2495

    • DOI

      10.1016/j.tet.2012.01.059

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A new approach to the synthesis of 1-oxaspiro[4.n]alkanes and tetrahydrofurans by the 1,5-CH insertion reaction of magnesium carbenoids2012

    • Author(s)
      Tsuyoshi Satoh
    • Journal Title

      Tetrahedron Letters

      Volume: 53 Issue: 16 Pages: 2074-2077

    • DOI

      10.1016/j.tetlet.2012.02.034

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] New synthesis of multi-substituted a-chlorocyclobutanones from 1-chloro-3-cycnoalkyl p-tolyl sulfoxides by 4-Exo-Dig nucleophilic ring closure of magnesium carbenoids to nitrile group as the key reaction2012

    • Author(s)
      Hideki Saitoh
    • Journal Title

      Tetrahedron Letters

      Volume: 53 Issue: 24 Pages: 3004-3008

    • DOI

      10.1016/j.tetlet.2012.03.127

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Quantum chemical characterization of magnesium carbenoids2012

    • Author(s)
      Tsutomu Kimura
    • Journal Title

      J. Organometal. Chem.

      Volume: 715 Pages: 1-4

    • DOI

      10.1016/j.jorganchem.2012.04.028

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent Advances in the Chemistry and Synthetic Uses of Magnesium carbenoids2012

    • Author(s)
      佐藤毅
    • Journal Title

      Heterocycles

      Volume: 85 Issue: 1 Pages: 1-33

    • DOI

      10.3987/rev-11-718

    • NAID

      40019137595

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Conjugated Enynes from Ketones and Aldehydes by 1,2-CC Insertion and 1,2-CH Insertion of Carbenoids as the Key Reactions2011

    • Author(s)
      N. Ishida, H. Saitoh, S. Sugiyama, T. Satoh
    • Journal Title

      Tetrahedron

      Volume: 67 Pages: 3081-3090

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Insertion of Cyclopropanes Between a Carbonyl Carbon and α-Carbon of Carbonyl Compounds with Cyclopropylmagnesium Carbenoids2011

    • Author(s)
      T. Satoh, G. Kashiwamura, S. Nagamoto, Y. Sasaki. S. Sugiyama
    • Journal Title

      Tetrahedron Lett.

      Volume: 52 Pages: 4468-4472

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Insertion of Cyclopropanes Between a Carbonyl Carbon and an α-Carbon--2011

    • Author(s)
      佐藤毅
    • Journal Title

      Tetrahedron Letters

      Volume: 52 Issue: 34 Pages: 4468-4472

    • DOI

      10.1016/j.tetlet.2011.06.069

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Conjugated Enynes from Ketones and Aldehydes by 1,2-CC Insertion2011

    • Author(s)
      佐藤毅
    • Journal Title

      Tetrahedron

      Volume: 67 Issue: 17 Pages: 3081-3090

    • DOI

      10.1016/j.tet.2011.02.079

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis, including asymmetric synthesis, of 1-substituted cyclopentene from cyclobutanones with one-carbon ring-expansion by……2011

    • Author(s)
      佐藤毅
    • Journal Title

      Tetrahedron

      Volume: 67 Pages: 1102-1113

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of multi-substituted cyclobutanes and alkylidenecyclobutanes by the reaction of cyclobutylmagnesium carbenoids with nucleophiles2011

    • Author(s)
      佐藤毅
    • Journal Title

      Synthesis

      Pages: 397-408

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A method for the synthesis of cyclopropanes by regiospecific and regio-selective magnesium carbenoid 1,3-CH insertion as the key reaction2010

    • Author(s)
      佐藤毅
    • Journal Title

      Tetrahedron

      Volume: 66 Pages: 5675-5686

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] 3-シアノアルキルマグネシウムカルベノイドの 4-Exo-Dig 型環化反応によるシクロブタノン類の合成2012

    • Author(s)
      三瓶太朗、齋藤英樹、加藤裕一、石田直行、佐藤 毅
    • Organizer
      第63回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      東京理科大学野田校舎
    • Year and Date
      2012-05-19
    • Related Report
      2012 Final Research Report
  • [Presentation] New Synthesis of Multi-substituted α-Chlorocyclobutanones2012

    • Author(s)
      佐藤毅
    • Organizer
      10th Symposium on Chemical Approach to Chirality
    • Place of Presentation
      東京理科大学森戸記念館
    • Year and Date
      2012-02-24
    • Related Report
      2011 Annual Research Report
  • [Presentation] Experimental and Theoretical Study of Magnesium Carbenoids2012

    • Author(s)
      木村 力、佐藤 毅
    • Organizer
      12thInternational Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
    • Place of Presentation
      京都
    • Related Report
      2012 Final Research Report
  • [Presentation] 四員環マグネシウムカルベノイドと芳香族アルコール類による spiro[3.6]deca- dienone 類の合成2011

    • Author(s)
      佐々木佑樹、永元しのぶ、佐藤 毅
    • Organizer
      第62回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      新潟大学
    • Year and Date
      2011-11-26
    • Related Report
      2012 Final Research Report
  • [Presentation] マグネシウムカルベノイドの置換反応および挿入反応によるシアノシクロプロパンの合成2011

    • Author(s)
      渡邊辰也、齋藤英樹、木村 力、加藤裕一、佐藤 毅
    • Organizer
      第65回香料テルペン精油化学に関する討論会
    • Place of Presentation
      つくば大学
    • Year and Date
      2011-11-09
    • Related Report
      2012 Final Research Report
  • [Presentation] シクロプロピルマグネシウムカルベノイドの遠隔CH挿入反応による環状化合物の合成2011

    • Author(s)
      鶴 隆広、池田尚太郎、佐藤 毅
    • Organizer
      第61回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      千葉大学
    • Year and Date
      2011-05-22
    • Related Report
      2012 Final Research Report
  • [Presentation] The chemistry of magnesium carbenoid and asymmetric synthesis2010

    • Author(s)
      佐藤毅
    • Organizer
      6^<th> Symposium on Chemical Approach to Chirality
    • Place of Presentation
      Tokyo
    • Year and Date
      2010-12-01
    • Related Report
      2010 Annual Research Report
  • [Presentation] マグネシウムカルベノイドの転位反応を鍵反応とする共役エンイン化合物の新規合成法2010

    • Author(s)
      石田直行、齋藤英樹、佐藤 毅
    • Organizer
      第36回反応と合成の進歩シンポジウム
    • Place of Presentation
      名古屋
    • Year and Date
      2010-11-01
    • Related Report
      2012 Final Research Report
  • [Presentation] シクロブチルマグネシウムカルベノイドを鍵中間体とする多置換シクロブタン類の合成2010

    • Author(s)
      石垣雅士、糟谷孝志、佐藤 毅
    • Organizer
      第64回香料テルペン精油化学に関する討論会
    • Place of Presentation
      山梨大学
    • Year and Date
      2010-10-23
    • Related Report
      2012 Final Research Report
  • [Presentation] 光学活性なジクロロメチルp-トリルスルホキシドを不斉源とするアレン類の不斉合成2010

    • Author(s)
      百地 仁、野口祟史、宮川利文、佐藤 毅
    • Organizer
      第59回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      東京農工大学工学部
    • Year and Date
      2010-05-22
    • Related Report
      2012 Final Research Report
  • [Presentation] Magnesium carbenoids: Synthetic application and theoretical study

    • Author(s)
      Tsutomu Kimura
    • Organizer
      11th Symopsium on chemical approach to chirality
    • Place of Presentation
      東京理科大学森戸記念館
    • Related Report
      2012 Annual Research Report
  • [Presentation] 1-クロロビニルスルホキシドを用いたシクロプロパンカルボン酸エステル類の新規合成法

    • Author(s)
      服部芳明
    • Organizer
      第56回香料テルペン精油化学討論会
    • Place of Presentation
      鹿児島大学
    • Related Report
      2012 Annual Research Report
  • [Presentation] 種々のマグネシウムカルベノイドとスルホン類を利用した多様な共役ジエン化合物の合成

    • Author(s)
      犬丸未央
    • Organizer
      第56回香料テルペン精油化学討論会
    • Place of Presentation
      鹿児島大学
    • Related Report
      2012 Annual Research Report
  • [Presentation] 1-クロロビニルスルホキシドとリチウムアセチリドを用いた共役不飽和化合物の合成

    • Author(s)
      西村有加
    • Organizer
      第56回香料テルペン精油化学討論会
    • Place of Presentation
      鹿児島大学
    • Related Report
      2012 Annual Research Report
  • [Presentation] Optically active dichloromethyl p-tolyl sulfoxide: Configurational stability --

    • Author(s)
      鶴 隆広
    • Organizer
      12th International Kyoto Conference on New Aspect of Organic Chemistry
    • Place of Presentation
      京都テレサ
    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

      http://WWW.rs.kagu.tus.ac.jp/~satohlab/

    • Related Report
      2012 Final Research Report

URL: 

Published: 2010-08-23   Modified: 2019-07-29  

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