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2006 Fiscal Year Final Research Report Summary

DESIGN AND SYNTHESIS OF NOVEL EXCITATORY AMINO ACIDS BASED ON THE TOTAL SYNTHESIS OF NATURAL NEE TROTOXTNS

Research Project

Project/Area Number 16201045
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Living organism molecular science
Research InstitutionOsaka City University

Principal Investigator

OHFUNE Yasufltnii  Osaka City University, GRADUTATE SCOOL OF SCIENCE, PROFESSOR (20142078)

Co-Investigator(Kenkyū-buntansha) SHINADA Tetsuro  OSAKA CITY UNIVERSITY, GRADUTATE SCOOL OF SCIENCE, ASSOCIATE PROFESSOR (30271513)
Project Period (FY) 2004 – 2006
Keywordsnatural neurotoxin / glutamate receptors / ion channel blocker / asymmetric Strecker synthesis / kaitocephalin / tetrodotoxin / 5,6,11-trideoxytetrodotoxin / squaryl group containing glutamate
Research Abstract

Naturally occurring neurotoxins possess polar functional groups in their structures corresponding to those of internal ligands of receptors, ion channels, and enzymes. These functional groups bind to these proteins through ionic or hygrogen bondings. In this research, we investigated the synthesis of neurotoxic natural products, kaitocephalin, an antagonist of ionotropic glutamate receptors, and 5,6,11-trideoxytetrodotoxin, a congener of tetrodotoxin family which is a potent Na+ channel blocker, and novel squaric acid-containing glutamate analogs. The total syntheses of kaitocephalin and 5, 6, 11-trideoxytetrodotoxin were achieved by the stereoselective construction of the quarternary carbon center using an asymmetric version of the Strecker synthesis, and subsequent assembly of the requisite multi-functional groups. The C7 and C9 diastereomers of kaitocephalin were also synthesized and subjected to SAR studies. The 13C-labelled 5, 6, 11-trideoxytetrodotoxin was also synthesized to exploit the biosynthetic pathway of tetrodotoxin as well as to elucidate molecular functions of the Na+ channel. Since squaric acid can be viewed as an equivalent of carboxylic acid, this group was incorporated into L-glutamate instead of its C1 or C5 carboxyl group. Among several squaryl glutamates synthesized in this study, it was found that a sulfur-linked analog exhibited potent and selective activity to kainic acid (KA) subtype receptors, suggesting that the squaryl group-containing glutamate analogs can be used as a useful tool to investigate glutamate receptors.

  • Research Products

    (52 results)

All 2007 2006 2005 2004

All Journal Article (50 results) (of which Peer Reviewed: 24 results) Book (2 results)

  • [Journal Article] Synthesis of Leucine-enkephalin Analogs Containing α-Amino Squaric Acids2007

    • Author(s)
      T. Shinada, T. Ishida, K. Hayashi, Y. Yoshida, Y. Shigeri, and Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 7614-7617

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed Intramolecular Olefin Insertion Reaction of α-Alkenyl-α-acyloxytrialkylsilane. Synthesis of Optically Active Carbocycles2007

    • Author(s)
      K. Sakaguchi, T. Okada, T. Yamada, and Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 3925-3928

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Ester-Enolate Claisen Rearrangement of Proline-Containing α-Acyloxy-α-vinylsilane. Synthesis of Pyrrolidine-fused Glutamate Anlogs2007

    • Author(s)
      K. Sakaguchi, M. Yamamoto, Y. Watanabe, and Y, Ohfune
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 4821-4824

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Synthesis and Absolute Structure of Manzacidin B2007

    • Author(s)
      T. Shinada, E. Ikebe, h. Oe, K. Namba, M. Kawasaki, and Y. Ohfune
    • Journal Title

      Org. Lett. 9

      Pages: 1765-1767

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Recent Progress on Squaric Acid Research in Bioorganic Fields2007

    • Author(s)
      T. Shinada, T. Ishida, and Y. Ohfune
    • Journal Title

      J. Synth. Org. Chem. Jpn. 65

      Pages: 30-45

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Efficient Asymmetric Synthesis of Novel 4-Substituted and Configurationally Stable Analogs of Thalidomide.2007

    • Author(s)
      T. Yamada, T. Okada, K. Sakaguchi, Y. Ohfune, H. Ueki, and V.A. Soloshonok
    • Journal Title

      Org. Lett. 9

      Pages: 5625-5628

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Synthesis of Leucine-enkephalin Analogs Containing a-Amino Squaric Acids2007

    • Author(s)
      T. Shinada, T. Ishida, K.-i. Hayashi, Y. Yoshida, Y. Shigeri, Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 7614-7617

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Ester-Enolate Claisen Rearrangement of Proline- Containing a-Acyloxy-a-vinylsilane. Synthesis of Pyrrolidine-fused Glutamate Analogs2007

    • Author(s)
      K. Sakaguchi, M. Yamamoto, Y. Watanabe, Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 4821-4824

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Palladium-catalyzed Intramolecular Olefin Insertion Reactionof a-Alkenyl-a-acyloxytrialkylsilane. Synthesis of Optically Active Carbocycles.2007

    • Author(s)
      K. Sakaguchi, T. Okada, T. Yamada, Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 3925-3928

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis and Absolute Structure of Manzacidin B.2007

    • Author(s)
      T. Shinada, E. Ikebe, K. Oe, K. Namba, M. Kawasaki, Y. Ohfune
    • Journal Title

      Org. Lett. 9

      Pages: 1765-1767

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Recent Progress on Squaric Acid Research in Bioorganic Fields2007

    • Author(s)
      T. Shinada, T. Ishida, Y. Ohfune
    • Journal Title

      J. Synth. Org. Chem. Jpn. 65

      Pages: 30-45

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Design, Synthesis and Evaluation of a New Generation of Modular Nucleophilic Glycine Equivalents for the Efficient Synthesis of Sterically Constrained α-Amino Acids.2006

    • Author(s)
      T. K. Ellis, H. Ueki, T. Yamada, Y. Ohfune, and V. A. Soloshonok
    • Journal Title

      J. Org. Chem. 71

      Pages: 8572-8578

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Novel Biologically Active Peptides from the Venom of Polistes rothneyi iwatai.2006

    • Author(s)
      K. Murata, T. Shinada, Y. Ohfune, M. Hisada, A. Yasuda, H. Naoki, and T. Nakajima
    • Journal Title

      Biol. Pharm. Bull. 29

      Pages: 2493-2497

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Total Synthesis of 5,6,11-Trideoxytetrodotoxin and its 4-Epimer.2006

    • Author(s)
      T. Umezawa, T. Hayashi, H. Sakai, H. Teramoto, T. Yoshikawa, M. Izumida, Y. Tamatani, T. Hirose, Y. Ohfune, and T. Shinada
    • Journal Title

      Org. Lett. 8

      Pages: 4971-4974

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Operationlly Convenient, Efficient Asymmetric Synthesis of Eenantiomerically Pure 4-Aminoglutamic Acids via Methylene Dimerization of Chiral Glycine Equivalents with Dichlorometthane2006

    • Author(s)
      V. A. Soloshonok, T. Yamada, H. Ueki, A. M. Moore, T. K. Cook, K. L. Arbogast, A. V. Soloshonok, C.H. Martin, and Y. Ohfune
    • Journal Title

      Tetrahedron 62

      Pages: 6412-6419

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] on the Stereoselectivity of the Asymmetric Strecker Synthesis in Cyclohexane System: Synthesis of Optically Active Cis-and Trans-1-Amino-2-hydroxycyclohexane-1-carboxylic Acids.2006

    • Author(s)
      T, Shinada, T, Kawakami, T. Umezawa, H. Matsuda, M, Kawasaki, K, Namba, and Y, Ohfune
    • Journal Title

      Bull. Chem. Soc. Jpn. 79

      Pages: 768-774

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] A New Entry for the Synthesis of N-Acyl-N'-Substituted Guanidine.2006

    • Author(s)
      T. Shinada, T. Umezawa, T. Ando, H. Kozuma, and Y. Ohfune
    • Journal Title

      Tetrrahedron Lett. 47

      Pages: 1945-1947

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] 天然神経毒とカイトセファリンの全合成2006

    • Author(s)
      大船 泰史
    • Journal Title

      ファルマシア(Farumashia) 42

      Pages: 817-821

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Efficient Asymmetric Synthesis of Novel 4-Substituted and Configurationally Stable Analogs of Thalidomide2006

    • Author(s)
      T. Yamada, T. Okada, K. Sakaguchi, Y. Ohfune, H. Ueki, V. A. Soloshonok
    • Journal Title

      Org. Lett. 8

      Pages: 5625-5628

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Design, Synthesis and Evaluation of a New Generation of Modular Nucleophilic Glycine Equivalents for the Efficient Synthesis of Sterically Constrained a-Amino Acids2006

    • Author(s)
      T. K. Ellis, H. Ueki, T, Yamada, Y. Ohfune, V. A. Soloshonok
    • Journal Title

      J. Org. Chem. 17

      Pages: 8572-8578

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Novel Biologically Active Peptides from the Venom of Polistes rothneyi iwatai.2006

    • Author(s)
      K. Murata, T. Shinada, Y. Ohfune, M. Hisada, A. Yasuda, H. Naoki, T. Nakajima
    • Journal Title

      Biol. Pharm. Bull. 29

      Pages: 2493-2497

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Total Synthesis of 5,6,11-Trideoxytetrodotoxir and its 4-Epimer.2006

    • Author(s)
      T. Umezawa, T. Hayashi, H. Sakai, H. Teramoto, T. Yoshikawa, M. Izumida, Y. Tamatani, T. Hirose, Y. Ohfune, T. Shinada
    • Journal Title

      Org. Lett. 8

      Pages: 4971-4974

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Operationally Convenient, Efficient Asymmetric Synthesis of EnantiomericallyPure 4-Aminoglutamic Acids viaMethylene Dimerization of Chiral Glycine Equivalents with Dichloromethane.2006

    • Author(s)
      V. A. Soloshonok, T. Yamada, H. Ueki, A. M. Moore, T. K. Cook, K. L. Arbogast, A. V. Soloshonok, C. H. Martin, Y. Ohfune
    • Journal Title

      Tetrahedron 62

      Pages: 6412-6419

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] On the Stereo- selectivity of the Asymmetric Strecker Synthesis in Cyclohexane System: Synthesis of Optically Active Cis- and Trans-1-amino-2-hydroxy cycl.ohexane-1-carboxylic Acids2006

    • Author(s)
      T. Shinada, T. Kawakami, T. Umezawa, H. Matsuda, M. Kawasaki, K. Namba, Y. Ohfune
    • Journal Title

      Bull. Chem. Soc. Jpn. 79

      Pages: 768-774

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A New Entry for the Synthesis of N-Acyl- N'-Substituted Guanidine.2006

    • Author(s)
      T. Shinada, T. Umezawa, T. Ando, H. Kozuma, Y. Ohfune
    • Journal Title

      Tetrrahedron Lett. 47

      Pages: 1945-1947

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Naturall Occarring Neurotoxins and Total Synthesis of Kaitocephalin.2006

    • Author(s)
      Y. Ohfune
    • Journal Title

      Farumashia 42

      Pages: 817-821

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Stereoselective Synthesis of 2,5-Di-and 2,2,5-Trisubstituted Pyrrolidines by Allylation Reaction of Acyl Imminiuln Ion.2005

    • Author(s)
      T. Shinada, M. Hamada, M. Kawasaki, and Y. Ohfune
    • Journal Title

      Heterocycles 66

      Pages: 511-525

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Micheal Addition Reactions Between Chiral Equivalents of a Nucleophilic Glycine and (S)-or (R)-4-phenyl-1,3-oxazolid in-2-ones s General method for Efficiewnt Preparation of b-Substituted Pyroglutamic Acids. Cases of Topographically Controlled Stereoselectivity.2005

    • Author(s)
      V. A. Soloshonok, C. Cai, T. Yamada, H, Ueki, Y. Ohfune, and V. J. Hruby
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 15296-15303

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Enantio- and Diastereoselective Construction of α,α-Disubstituted α-Amino Acid for the Synthesis of Biologically Active Compounds.2005

    • Author(s)
      Y. Ohfune and T. Shinada
    • Journal Title

      Eur. J. Org. Chem.

      Pages: 5127-5143

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Allylic Alkylation of Optically Active α-Alkenyl-α-acyloxytrialkylsilane.2005

    • Author(s)
      K. Sakaguchi, T. Yamada, and Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 46

      Pages: 5009-5012

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Total Synthesis of (-)-Kaitocephalin.2005

    • Author(s)
      M. Kawasaki, T. Shinada, M. Hamada, and Y. Ohfune
    • Journal Title

      Org. Lett. 7

      Pages: 4165-4167

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Alternative Synthetic Route to Access α-Amino Squaric Acid using Alninomalonate Equivalent bearing Squaryl Group.2005

    • Author(s)
      T. Shinada, T. Ishida, and Y. Ohfune
    • Journal Title

      Synthesis

      Pages: 2723-2729

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Molecular Compounds and Toxicity of the Venom of the Solitary Wasp, Anoplius samariensis.2005

    • Author(s)
      M. Hisada, H. Satake, K. Masuda, M. Aoyama, K. Murata, T. Shinada, T. Iwashita, Y. Ohfune, and T.Nakajima
    • Journal Title

      BBRC: Biochem. Biophys. Res. Commun. 330

      Pages: 1048-1054

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Indium-mediateed Barbier-type Allylation of Aldimnes in AIcoholic Media: Synthesis of Optically Active Homoallylamines.2005

    • Author(s)
      Tirayut Viraivan, Chutima Winotapan, T. Shinada, and Y. Ohfune
    • Journal Title

      J. Org. Chem. 70

      Pages: 3464-3471

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Application of Modular Nucleophilic Glycine Equivalents for Truly Practical Asymmetric Synthesis of β-Substituted Pytoglutamic Acids.2005

    • Author(s)
      V. A. Soloshonok, H. Ueki, T. K. Ellis, T. Yamada, and Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 46

      Pages: 1107-1110

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Synthesis of Novel Amino Squaric Acid via Addition of Dianion Enolate Derived from N-Boc Amino Acid Esters.2005

    • Author(s)
      T. Ishida, T. Shinada, and Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 46

      Pages: 311-314

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Stereoselective Synthesis of 2,5-Di- and 2,2,5-Trisubstituted Pyrrolidines by Allylation Reaction of Acyl Imminium Ion.2005

    • Author(s)
      T. Shinada, M. Hamada, M. Kawasaki, Y. Ohfune
    • Journal Title

      Heterocycles 66

      Pages: 511-525

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Micheal Addition Reactions Between Chiral Equivalents of a Nucleophilic Glycine and (5)-or (R)-4-phenyl-1,3-oxazolidin-2-ones. General method for Efficiewnt Preparation of (3-Substituted Pyroglutamic Acids. Cases of Topographically Controlled Stereoselectivity.2005

    • Author(s)
      V. Soloshonok, C. Cai, T. Yamada, H. Ueki, Y. Ohfune, V. J. Hruby
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 15296-15303

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enantio- and Diastereo- selective Construction of a,a-Disubstituted a-Amino Acid for the Synthesis of Biologically Active Compounds.2005

    • Author(s)
      Y. Ohfune, T. Shinada
    • Journal Title

      Eur. J. Org. Chem.

      Pages: 5127-5143

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Palladium-Catalyzed Allylic Allylation of OpticallyActive a-Alkenyl-a-acyloxytrialkylsilane.2005

    • Author(s)
      K. Sakaguchi, T. Yamada, Y. Ohfune
    • Journal Title

      Tetrahedron Lett 46

      Pages: 5009-5012

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Total Synthesis of (-)-Kaitocephalin2005

    • Author(s)
      M. Kawasaki, T. Shinada, M. Hamada, Y. Ohfune
    • Journal Title

      Org. Lett. 7

      Pages: 4165-4167

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Alternative Synthetic Route to Access a-Amino Squaric Acid using Aminomalonate Equivalent bearing Squaryl Group.2005

    • Author(s)
      T. Shinada, T. Ishida, Y. Ohfune
    • Journal Title

      Synthesis

      Pages: 2723-2729

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Molecular Compounds and Toxicity of the Venom of the Solitary Wasp, Anoplius samariensis.2005

    • Author(s)
      M. Hisada, H. Satake, K. Masuda, M. Aoyama, K. Murata, T. Shinada, T. Iwashita, Y. Ohfune, T. Nakajima
    • Journal Title

      BBRC: Biochem. Biophys. Res. Coinlnun. 330

      Pages: 1048-1054

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Indium-mediateed Barbier-type Allylation of Aldimnes in Alcoholic Media: Synthesis of Optically Active Homoallylamines.2005

    • Author(s)
      T. Viraivan, C. Winotapan, T. Shinada, Y. Ohfune
    • Journal Title

      J. Org. Chem. 70

      Pages: 3464-3471

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Application of Modular Nucleophilic Glycine Equivalents for Truly Practical Asymmetric Synthesis of β-Substituted Pyroglutamic Acids.2005

    • Author(s)
      V. A. Soloshonok, H. Ueki, T. K. Ellis, T. Yamada, Y. Ohfune
    • Journal Title

      Tetrahedron Lett 46

      Pages: 1107-1110

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Novel Amino Squaric Acid via Addition of Diapion Enolate Derived from N-Boc Amino Acid Esters.2005

    • Author(s)
      T. Ishida, T. Shinada, Y. Ohfune
    • Journal Title

      Tetrahedron Lett. 46

      Pages: 311-314

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Optically Active β-Alkyl Aspartate via [3,3] Sigmatropic Rearrangement of α-Acyloxytrialkylsilane.2004

    • Author(s)
      K. Sakaguchi, M. Yamamoto, T. Kawamoto, T. Yamada, T. Shinada, K. Shimamoto, and Y. Ohfune
    • Journal Title

      Tetrahedron Lett 45

      Pages: 5869-5872

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] ヘテロ環状立体制御に基づくα-置換アミノ酸類の不斉合成2004

    • Author(s)
      大船 泰史、品田 哲郎
    • Journal Title

      化学工業 55

      Pages: 138-145

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Optically Active f3-Alkyl Aspartate via [3,3] Sigmatropic Rearrangement of a-Acyloxytrialkylsilane.2004

    • Author(s)
      K. Sakaguchi, M. Yamamoto, T. Kawamoto, T. Yamada, T. Shinada, K. Shimamoto, Y. Ohfune
    • Journal Title

      Tetrahedron Lett 45

      Pages: 5869-5872

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric Synthesis of a-Substituted a-Amino Acids Nassed on the Heterocyclic Stereocontrol.2004

    • Author(s)
      Y. Ohfune, T. Shinada
    • Journal Title

      Kagaku-Kogyo 55

      Pages: 138-145

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] 第5版実験化学講座、16巻、2章2.1-2.3節「アミノ酸・ペプチド」2005

    • Author(s)
      大船、坂口、品田
    • Total Pages
      43
    • Publisher
      丸善
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] 化学便覧改訂5版(日本化学会編)、基礎編1第4章3節1項「生体アミン類」2004

    • Author(s)
      大船
    • Total Pages
      5
    • Publisher
      丸善
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2010-02-04  

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