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Catalytic Asymmetric Synthesis of Chiral Cyclic Ethers

Research Project

Project/Area Number 22750088
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionNagoya University

Principal Investigator

TANAKA Shinji  名古屋大学, 物質科学国際研究センター, 助教 (00529034)

Project Period (FY) 2010 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2011: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2010: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords環状工一テル / 不斉アリル化 / 脱水反応 / ルテニウム / 環状エーテル / 不斉反応 / πアリル
Research Abstract

Chiral cyclic ethers constitute one of the most important structural units in biologically active compounds. Among many key building blocks reported so far, a-alkenyl-substituted cyclic ethers are widely recognized as the most useful because the alkenyl moiety can be transformed to a wide range of functionalities. In particular, the focal point is the creation of catalytic enantioselective protocols. Here, we focused on a new type of protocol, in which non-activated or non-protected ow-hydroxy allyl alcohols dehydratively cyclize to the corresponding cyclic ethers.
Based on the information that a catalytic system combined[CpRu(CHsCN) 3] PF6 with a pyridine-2-carboxylic acid derivative or the corresponding cationic CpRu(IV)-st-allyl carboxylato complex which can convert a 1 : 1 mixture of alcohols and allyl alcohols to allyl ethers with the liberation of water, we developed a new chiral ligand, s-methyl-6-(2-R-naphthalen-l-yl)-pyridine-2-carboxylic acid(R-Naph-PyCOOH). The ligand is characterized by the sterically flexible axial chirality through C(6)-C(1') bond and the adjustability of electronic and steric properties of the naphthalene ring by the R substituent at C(2'). As the result of an investigation of ligand structure-reactivity and selectivity relationships, the combination of Cl-Naph-PyCOOH or its allyl ester with a CpRu complex achieves the cyclization with excellent reactivity and selectivity, giving various a-alkenyl-substituted cyclic ethers, such as tetrahydrofuran, tetrahydro-2H-pyran, coumaran, and chromane, with up to> 99 : 1 enantiomer ratio.

Report

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

    (52 results)

All 2012 2011 2010 Other

All Journal Article (8 results) (of which Peer Reviewed: 5 results) Presentation (38 results) Book (1 results) Remarks (1 results) Patent(Industrial Property Rights) (4 results) (of which Overseas: 2 results)

  • [Journal Article] Enantioselective Synthesis of Pyrrolidine-, Piperidine-, and Azepane-Type N-Heterocycles with a-Alkenyl Substitution : The CpRu-Catalyzed Dehydrative Intramolecular N-Allylation Approach2012

    • Author(s)
      T. Seki, S. Tanaka, M. Kitamura
    • Journal Title

      Org. Lett.

      Volume: 14 Pages: 608-611

    • Related Report
      2011 Final Research Report
  • [Journal Article] Enantioselective Synthesis of Pyrrolidine-, Piperidine-, and Azepane-Type N-Heter ocycles with α-Alkenyl Substitution : The CpRu-Catalyzcd Dehydrative Intramolecular N-Allylation Approach2012

    • Author(s)
      Seki, T.; Tanaka, S.; Kitamura, M.
    • Journal Title

      Org.Lett.

      Volume: 14 Pages: 608-611

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Dehydrative S-Allylation of Cysteine-Containing Peptides in Aqueous Media toward Lipopeptide Chemistry2011

    • Author(s)
      P. Jaisankar, S. Tanaka, and M. Kitamura
    • Journal Title

      J. Org. Chem

      Volume: 76 Pages: 1894-1897

    • Related Report
      2011 Final Research Report
  • [Journal Article] Catalytic Dehydrative S-Allylation of Cysteine-Containing Peptides in Aqueous Media toward Lipopeptide Chemistry2011

    • Author(s)
      Jaisankar, P.; Tanaka, S.; Kitamura, M.
    • Journal Title

      J.Org.Chem.

      Volume: 76 Issue: 6 Pages: 1894-1897

    • DOI

      10.1021/jo102278m

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Dehydrative S-Allylation of Cysteine-Containing Peptides in Aqueous Media toward Lipopeptide Chemistry2011

    • Author(s)
      P.Jaisankar, S.Tanaka, M.Kitamura
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 76 Pages: 1894-1897

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium(1+), (5-2,4-Cyclopentadien-1-yl)(3-2 propen-1-yl)(2-quinolinecarboxylato-N1,02)-, Hexafluorophosphate(1-) (1:1)2011

    • Author(s)
      S.Tanaka, M.Kitamura
    • Journal Title

      e-EROS

      Volume: (On-line)

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Highly Efficient Catalytic Dehydrative S-Allylation of Thiols and Thioic S-Acids2010

    • Author(s)
      S. Tanaka, P. K. Pradhan, Y. Maegawa, and M. Kitamura
    • Journal Title

      Chem. Commun

      Volume: 46 Pages: 3996-3998

    • Related Report
      2011 Final Research Report
  • [Journal Article] Highly Efficient Catalytic Dehydrative S-Allylation of Thiols and Thioic S-Acids2010

    • Author(s)
      S.Tanaka, P.K.Pradhan, Y.Maegawa, M.Kitamura
    • Journal Title

      Chemical Communications

      Volume: 46 Pages: 3996-3998

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] 光学活性ピコリン酸型配位子を有するカチオン性CpRu錯体を用いる脱水型触媒的不斉アリル化の機構2012

    • Author(s)
      関知昭・田中慎二・北村雅人
    • Organizer
      日本薬学会第92春季年会
    • Place of Presentation
      札幌
    • Year and Date
      2012-03-30
    • Related Report
      2011 Final Research Report
  • [Presentation] 光学活性ピコリン酸型配位子を有するカチオン性CpRu錯体を用いる脱水型触媒的不斉アリル化の機構2012

    • Author(s)
      関知昭、田中慎二、北村雅人
    • Organizer
      日本薬学会第132年会
    • Place of Presentation
      日本薬学会第132年会
    • Year and Date
      2012-03-30
    • Related Report
      2011 Annual Research Report
  • [Presentation] CpRu-2-キノリンカルボン酸触媒を用いる脱水的S-アリル化2012

    • Author(s)
      田中慎二・PRADHAN P. K.・北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-28
    • Related Report
      2011 Final Research Report
  • [Presentation] CpRu-2-キノリンカルボン酸触媒を用いる脱水的S-アリル化2012

    • Author(s)
      田中慎二、PRADHAN P.K.、北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大
    • Year and Date
      2012-03-28
    • Related Report
      2011 Annual Research Report
  • [Presentation] リポペプチド合成に向けたシステイン含有ペプチド類の脱水的S-アリル化2012

    • Author(s)
      田中慎二・二田由香里・JAISANKAR P.・北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-27
    • Related Report
      2011 Final Research Report
  • [Presentation] メソ型ジヒドロキシビスアリルアルコール類の非対称化2012

    • Author(s)
      青山悟・葛西達也・田中慎二・北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-27
    • Related Report
      2011 Final Research Report
  • [Presentation] 新規光学活性ピコリン酸配位子の合成2012

    • Author(s)
      松下雅晴・伊代田陽子・関知昭・田中慎二・北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-27
    • Related Report
      2011 Final Research Report
  • [Presentation] 新規光学活性ピコリン酸配位子の合成2012

    • Author(s)
      松下雅晴、伊代田陽子、関知昭、田中慎二、北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2012-03-27
    • Related Report
      2011 Annual Research Report
  • [Presentation] メソ型ジヒドロキシビスアリルアルコール類の非対称化2012

    • Author(s)
      青山悟、葛西達也、田中慎二、北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2012-03-27
    • Related Report
      2011 Annual Research Report
  • [Presentation] リポペプチド合成に向けたシステイン含有ペプチド類の脱水的S-アリル化2012

    • Author(s)
      田中慎二、二田由香里、JAISANKAR P.、北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2012-03-27
    • Related Report
      2011 Annual Research Report
  • [Presentation] CpRu一ピコリン酸触媒を用いる脱水型分子内不斉アリル化の機構2012

    • Author(s)
      関知昭・里中慎二・北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-26
    • Related Report
      2011 Final Research Report
  • [Presentation] 光学活性sp^2窒素系二座配位子Naph-diPIM金属錯体の合成2012

    • Author(s)
      宮田健吾・二田由香里・田中慎二・北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-26
    • Related Report
      2011 Final Research Report
  • [Presentation] 光学活性sp2窒素系二座配位子Naph-diPIM金属錯体の合成2012

    • Author(s)
      宮田健吾、二田由香里、田中慎二、北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2012-03-26
    • Related Report
      2011 Annual Research Report
  • [Presentation] CpRu-ピコリン酸触媒を用いる脱水型分子内不斉アリル化の機構2012

    • Author(s)
      関知昭、伊代田陽子、田中慎二、北村雅人
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2012-03-26
    • Related Report
      2011 Annual Research Report
  • [Presentation] 光学活性ピコリン酸型配位子Cl-Naph-PyCOOH :脱水型不斉アリル化への応用2011

    • Author(s)
      関知昭・青山悟・松下雅晴・伊代田陽子・田中慎二・北村雅人
    • Organizer
      第46回天然物化学談話会
    • Place of Presentation
      静岡
    • Year and Date
      2011-07-07
    • Related Report
      2011 Final Research Report
  • [Presentation] 光学活性ピコリン酸型配位子Cl-Naph-PyCOOH:脱水型不斉アリル化への応用2011

    • Author(s)
      関知昭、青山悟、松下雅晴、伊代田陽子、田中慎二、北村雅人
    • Organizer
      第46回天然物化学談話会
    • Place of Presentation
      静岡
    • Year and Date
      2011-07-07
    • Related Report
      2011 Annual Research Report
  • [Presentation] Catalytic Dehydrative S-Allylation of Thiols and Thioic S-Acids2011

    • Author(s)
      S. Tanaka, K. Miyata, M. Kitamura
    • Organizer
      The 1st International Conference on MEXT Project of Integrated Research on Chemical Synthesis
    • Place of Presentation
      Sapporo
    • Year and Date
      2011-01-24
    • Related Report
      2011 Final Research Report 2010 Annual Research Report
  • [Presentation] Dehydrative Allylation of Alcohols and Deallylation of Allyl Ethers Catalyzed by[CpRu(CH_3CN)_3] PF_6 and 2-Pyridinecarboxylic Acid Derivatives. Effect of it-Accepting Ability and COOH Acidity of Ligand on Reactivity2011

    • Author(s)
      T. Seki, S. Tanaka, M. Kitamura
    • Organizer
      The 1st International Conference on MEXT Project of Integrated Research on Chemical Synthesis
    • Place of Presentation
      Sapporo
    • Year and Date
      2011-01-24
    • Related Report
      2011 Final Research Report
  • [Presentation] Dehydrative Allylation of Alcohols and Deallylation of Allyl Ethers Catalyzed by [CpRu(CH_3CN)_3]PF_6 and 2-Pyridinecarboxylic Acid Derivatives. Effect of π-Accepting Ability and COOH Acidity of Ligand on Reactivity2011

    • Author(s)
      T.Seki, S.Tanaka, M.Kitamura
    • Organizer
      The 1st International Conference on MEXT Project of Integrated Research on Chemical Synthesis
    • Place of Presentation
      Sapporo
    • Year and Date
      2011-01-24
    • Related Report
      2010 Annual Research Report
  • [Presentation] Dehydrative Allylation of Alcohols and Deallylation of Allyl Ethers Catalyzed by[CpRu(CH_3CN)_3] PF_6 and 2-Pyridinecarboxylic Acid Derivatives. Effect of z-Accepting Ability and COOH Acidity of Ligand on Reactivity2010

    • Author(s)
      S. Tanaka, T. Seki, H. Nakatsuka, and M. Kitamura
    • Organizer
      PACIFIC HEM 2010
    • Place of Presentation
      USA
    • Year and Date
      2010-12-18
    • Related Report
      2011 Final Research Report
  • [Presentation] Dehydrative Allylation of Alcohols and Deallylation of Allyl Ethers Catalyzed by [CpRu(CH_3CN)_3]PF_6 and 2-Pyridinecarboxylic Acid Derivatives. Effect of π-Accepting Ability and COOH Acidity of Ligand on Reactivity2010

    • Author(s)
      S.Tanaka, T.Seki, H.Nakatsuka, M.Kitamura
    • Organizer
      PACIFICHEM 2010
    • Place of Presentation
      Honolulu, USA
    • Year and Date
      2010-12-18
    • Related Report
      2010 Annual Research Report
  • [Presentation] Catalytic Dehydrative S-Allylation of Thiols and Thioic S-Acid2010

    • Author(s)
      S.Tanaka, P.K.Prasun, Y.Maegawa, M.Kitamura
    • Organizer
      PACIFICHEM 2010
    • Place of Presentation
      Honolulu, USA
    • Year and Date
      2010-12-18
    • Related Report
      2010 Annual Research Report
  • [Presentation] A New, Efficient and Direct Preparation of TlTp and Related Complexes with TlBH_42010

    • Author(s)
      M. Yoshimura, S. Tanaka, K. Tsuda, and M. Kitamura
    • Organizer
      PACIFIC HEM 2010
    • Place of Presentation
      USA
    • Year and Date
      2010-12-17
    • Related Report
      2011 Final Research Report
  • [Presentation] A New, Efficient and Direct Preparation of TlTp and Related Complexes with TlBH_42010

    • Author(s)
      M.Yoshimura, S.Tanaka, K.Tsuda, M.Kitamura
    • Organizer
      PACIFICHEM 2010
    • Place of Presentation
      Honolulu, USA
    • Year and Date
      2010-12-17
    • Related Report
      2010 Annual Research Report
  • [Presentation] Catalytic Dehydrative S-Allylation of Thiols and Thioic S-Acid2010

    • Author(s)
      S. Tanaka, P. K. Prasun, Y. Maegawa
    • Organizer
      PACIFIC HEM 2010
    • Place of Presentation
      USA
    • Year and Date
      2010-12-15
    • Related Report
      2011 Final Research Report
  • [Presentation] [CpRu(η^3-C_3H_5(2-pyridinecarboxylato)]-PF6 Complex Supported on a Ferromagnetic Microsize Particle Fe_3o_4@ Sio_22010

    • Author(s)
      S. Tanaka, T. Seki, Y. Minematsu, and M. Kitamura
    • Organizer
      PACIFIC HEM 2010
    • Place of Presentation
      USA
    • Year and Date
      2010-12-15
    • Related Report
      2011 Final Research Report
  • [Presentation] Enantioselective dehydrative catalytic cyclization of w-hydroxy allyl alcohols2010

    • Author(s)
      T. Seki, S. Aoyama, M. Matsushita, G. Salunke, S. Tanaka, and M. Kitamura
    • Organizer
      PACIFIC HEM 2010
    • Place of Presentation
      USA
    • Year and Date
      2010-12-15
    • Related Report
      2011 Final Research Report
  • [Presentation] Enantioselective dehydrative catalytic cyclization of ω-hydroxy allyl alcohols2010

    • Author(s)
      T.Seki, S.Aoyama, M.Matsushita, G.Salunke, S.Tanaka, M.Kitamura
    • Organizer
      PACIFICHEM 2010
    • Place of Presentation
      Honolulu, USA
    • Year and Date
      2010-12-15
    • Related Report
      2010 Annual Research Report
  • [Presentation] [CpRu(η^3-C_3H_5)(2-pyridinecarboxylato)]PF_6 Complex Supported on a Ferromagnetic Microsize Particle Fe_3O_4@SiO_22010

    • Author(s)
      S.Tanaka, T.Seki, Y.Minematsu, M.Kitamura
    • Organizer
      PACIFICHEM 2010
    • Place of Presentation
      Honolulu, USA
    • Year and Date
      2010-12-15
    • Related Report
      2010 Annual Research Report
  • [Presentation] 脱水型分子内不斉O一アリル化による光学活性オキサシクロアルカン類の触媒的合成2010

    • Author(s)
      関知昭・田中慎二・北村雅人
    • Organizer
      第45回天然物化学談話会
    • Place of Presentation
      蒲郡
    • Year and Date
      2010-07-06
    • Related Report
      2011 Final Research Report
  • [Presentation] 脱水型分子内不斉O-アリル化による光学活性オキサシクロアルカン類の触媒的合成2010

    • Author(s)
      関知昭・田中慎二・北村雅人
    • Organizer
      第45回天然物化学談話会
    • Place of Presentation
      蒲郡
    • Year and Date
      2010-07-06
    • Related Report
      2010 Annual Research Report
  • [Presentation] Asymmetric Synthesis of a-Alkenyl-substituted Cyclic Ethers2010

    • Author(s)
      T. Seki, S. Tanaka, and M. Kitamura
    • Organizer
      Global COE in Chemistry Annual Symposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-06-16
    • Related Report
      2011 Final Research Report 2010 Annual Research Report
  • [Presentation] A PNN-type Tridentate Linear Lig and : BINAN-Py-PPh_2-Its Application to Asymmetric Hydrogenation2010

    • Author(s)
      H. Nakatsuka, S. Tanaka, M. Yoshimura, and M. Kitamura
    • Organizer
      Global COE in Chemistry Annual Symposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-06-16
    • Related Report
      2011 Final Research Report
  • [Presentation] A PNN-type Tridentate Linear Ligand : BINAN-Py-PPh2 -Its Application to Asymmetric Hydrogenation-2010

    • Author(s)
      H.Nakatsuka, S.Tanaka, M.Yoshimura, M.Kitamura
    • Organizer
      Global COE in Chemistry Annual Symposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-06-16
    • Related Report
      2010 Annual Research Report
  • [Presentation] Asymmetric Intramolecular 0-allylation Using Cl-Naph-PyCOOAII/CpRu Combined Catalyst2010

    • Author(s)
      T. Seki, S. Tanaka, and M. Kitamura
    • Organizer
      IRTG Joint Synposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-05-25
    • Related Report
      2011 Final Research Report
  • [Presentation] sp^2N/sp^3N Combined Linear Ligands Ph-BINAN-H-Py and BINAN-Py-PPh2 : Stereo selectivity in Complexation with Octahedral Metals2010

    • Author(s)
      H. Nakatsuka, S. Tanaka, M. Yoshimura, and M. Kitamura
    • Organizer
      IRTG Joint Synposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-05-25
    • Related Report
      2011 Final Research Report
  • [Presentation] sp^2N/sp^3N Combined Linear Ligands Ph-BINAN-H-Py and BINAN-Py-PPh_2 : Stereoselectivity in Complexation with Octahedral Metals2010

    • Author(s)
      H.Nakatsuka, S.Tanaka, M.Yoshimura, M.kitamura
    • Organizer
      IRTG Joint Symposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-05-25
    • Related Report
      2010 Annual Research Report
  • [Presentation] Asymmetric Intramolecular O-allylation Using Cl-Naph-PyCOOAll/CpRu Combined Catalyst2010

    • Author(s)
      T.Seki, S.Tanaka, M.kitamura
    • Organizer
      IRTG Joint Symposium
    • Place of Presentation
      Nagoya
    • Year and Date
      2010-05-25
    • Related Report
      2010 Annual Research Report
  • [Book] Ruthenium(1+),(5-2, 4-Cyclopentadien-l-yl)-(η^3-2-propen-1-yl)(2-quinolinecarboxylato-N], O 2)-, Hexafluorophosphate(1)(1 : 1)2011

    • Author(s)
      S. Tanaka, and M. Kitamura
    • Related Report
      2011 Final Research Report
  • [Remarks]

    • URL

      http://www.os.rcms.nagoya-u.ac.jp/index.php

    • Related Report
      2010 Annual Research Report
  • [Patent(Industrial Property Rights)] 不斉合成触媒用配位子およびそれを用いたα一アルケニル環状化合物類の製造方法2010

    • Inventor(s)
      北村雅人,田中慎二
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Filing Date
      2010-10-01
    • Related Report
      2011 Final Research Report
    • Overseas
  • [Patent(Industrial Property Rights)] アリル化合物類の製造方法2010

    • Inventor(s)
      北村雅人,田中慎二
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Industrial Property Number
      2010-104529
    • Filing Date
      2010-04-28
    • Related Report
      2011 Final Research Report
  • [Patent(Industrial Property Rights)] 新規なルテニウム錯体を用いたアリル系保護基の除去方法及びアリルエーテル類の製造方法2010

    • Inventor(s)
      北村雅人,田中慎二,佐分元
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Industrial Property Number
      2005-027096
    • Filing Date
      2010-02-02
    • Related Report
      2011 Final Research Report
  • [Patent(Industrial Property Rights)] チオール類およびチオイック-S-アシッド類の触媒的脱水型アリル化2010

    • Inventor(s)
      北村雅人、田中慎二
    • Industrial Property Rights Holder
      名古屋大学
    • Industrial Property Number
      2010-104529
    • Filing Date
      2010-04-28
    • Related Report
      2010 Annual Research Report
    • Overseas

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Published: 2010-08-23   Modified: 2016-04-21  

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