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Creation of Fluorinated Amino Acids Library

Research Project

Project/Area Number 13555254
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Synthetic chemistry
Research InstitutionOKAYAMA UNIVERSITY

Principal Investigator

UNEYAMA Kenji  Okayama University, Graduate School, Faculty of Natural Science and Technology, Professor, 大学院・自然科学研究科, 教授 (00033150)

Co-Investigator(Kenkyū-buntansha) KATAGIRI Toshimasa  Okayama University, Graduate School, Faculty of Natural Science and Technology, Associate Professor, 大学院・自然科学研究科, 助教授 (70202009)
AMII Hideki  Okayama University, Graduate School, Faculty of Natural Science and Technology, Research Associate, 大学院・自然科学研究科, 助手 (00284084)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥13,500,000 (Direct Cost: ¥13,500,000)
Fiscal Year 2003: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2002: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 2001: ¥5,800,000 (Direct Cost: ¥5,800,000)
Keywordsamino acid / fluorine / defluorination / フッ素化 / 脱フッ素化 / フルオロアミノ酸
Research Abstract

In order to create a library of fluorinated amino acids, a basic study on magnesium-promoted C-F bond activation has been done and then several fluoorinated amino acids have been synthesized stereoselectively. The followings are a summary of the syntheses.
1) Syntheses of optically active β,β-difluoroproline(1) and β,β-difluoroglutamates(2
α-imino-β bromo-β,β-difluoropropanate was enantioselecdvely hydrogenated by Pd(OCOCF3)2 in trifluoroethanol to provide the corresponding amine in 87%ee, which was transformed to (1) and (2) by sequensial chemical reactions.
2) Syntheses of optically active α-trifluoromethyl-α-carboalkoxyaziridine (3)
Optically active α-trifluoromethylaziridine was lithiated in THF and carboalkoxylated with chloro formate in 95% yield with retention of the configuration. The aziridine could be ring-opened by the nucleuophiles leading to the general syntheses of α-trifluoromethylated amino acids.
3) Synthese of N, α-C-disilyl-β,β-difluoroenamines (4) and their utilization f … More or fluorinated amino acids
Mg-promoted C-F bond activation of trifluoroacetimidoyl chloride in THF provided of N, α-C-bissilyl-β,β-difluoroenamines in excellent yields, which are synthetic equivalents of N, α-C-and α-C-β-C-dianion. The bissilyl enamines could be allcylated stepwise leading to a vaiety of functionalized amino acid precursors.
4) Syntheses of optically active trifluoromethylnorcoronamc acids (5)
The intramolecular stereospecific substitution of hydroxy group with cyanide-stabilized carbanion provided optically active trifluoromethylcyclopropanes which could be transformed to amino acids (5).
5) Syntheses of trifluoromethylisocysteine(6)
Condensation of trifluoroacetimidoyl chloride with S-protected α-thioacetate followed by disstereoselective reduution of imono moiety and deprotection of thio moiety gave (6).
6) Rhodium catalyzed quinoline ring formation by the reaction of trifluoroacetimidoyl chloride with acetylene carboaylates provided quinoline carboxylates in one-pot reaction. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (52 results)

All Other

All Publications (52 results)

  • [Publications] Hajime Abe, Hideki Amii, Kenji Uneyama: "Pd-catalyzed Asymmetric Hydrogenation of α-Fluorinated Iminoesters in fluorinated Alcoho : a New and Catalytic Enantioselective Synthesis of Fluoro a-amino Acid Derivative"Org.Lett. 3. 313-315 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kenji Uneyama, Hironari Ohkura, Jian Hao, Hideki Amii: "A Trial toward the Synthesis of γ-Fluorinated-β- amino -a-thioamino Acids. A finding of Desulfurizative C-C Bond formation in thio-Wittig Rearrangement of S-(N-Aryltrifluoroacetimidoyl)thioglycolates."J.Org.Chem. 66. 1026-1029 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Youshuke Kishikawa, Kenji Uneyama: "Rh(I)-catalyzed Coupling Cyclization of N-Aryl Trifluoroacetimidoyl Chlorides with alkynes : One-pot Synthesis of Fluorinated Quinolines"Org.Lett.. 3. 1009-1112 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshimasa Katagiri, Michiharu Handa, Yasuhisa Matsukawa, J. S.Dileep Kumar, Kenji Uneyama: "Efficient Synthesis of an Optically Pure β-Bromo-β,β-difluoroalanine Derivative, a General Precursor for β,β-Difluoroamino Acids."Tetrahedron : Asymmetry. 12. 1303-1311 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Takeshi Kobayashi, Hiroshi Terasawa, Kenji Uneyama: "Difluorinated Danishefsky's Dienes : a Vasatile C4-building Block for the Fluorinated 6-Membered ring"Org.Lett.. 3. 3103-3105 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshimasa Katagiri, Sachiko Yamaji, Michiharu Handa, Minoru Irie, Kenji Uneyama: "Diastereoselectivity Controlled by Electrostatic Repulsion between the Negative Charge on a Trifluoromethyl Group and that on Aromatic Rings"Chem.Commun. 2054-2055 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshihiko Yamauchi, Toshimasa Katagiri, Kenji Uneyama: "The First Generation and Stereoselective Alkylation of a-Trifluoro-methyl Oxiranyl Anion."Org.Lett. 4. 173-176 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masayuki Mae, Makoto Matsuura, Hideki Amii, Kenji Uneyama: "A Facile Synthesis of Difluoromethylaziridines."Tetrahedron Lett.. 48. 2069-2072 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Horonari Ohkura, Michiharu Handa, Topshimasha Katagiri, Kenji Uneyama: "Diastereoselective Synthesis of S-tert-Butyl-(trifluoromethyl)-isocysteine."J.Org.Chem.. 67. 2692-2695 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshimasa Katagiri, Yasuyuki Fujiwara, Satoshi, Takahashi, Nobuyuki Ozaki, Kenji Uneyama: "Chiral Induction Controlled by aggregation of Organometallics ; Trifluoromethylated aminoalcohols for chiral Ligands Et2Zn Alkylation of Benzladehyde"Chem.Commun.. 986-987 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Vadim A.Soloshonok, Hironari Ohkura, Kenji Uneyama: "Biomimetic Reductive Amination of Perfluoroalkylcarboxylic Acids to α,α-Dihydroperfluoroalkylamines"Tetrahedron Lett.. 43. 5449-5452 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hiroshi Hata, Takeshi Kobayashi, Hideki Amii, Kenji Uneyama, John T.Welch: "A New Sequential Defluorination route to α-Fluoro-α,β-unsaturated ketones from trifluorom ethyl Ketones"Tetraheron Lett.. 43. 6099-6102 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Satoru Kobayashi, Hiroaki Tanaka, Hideki Amii, Kenji Uneyama: "A New Finding in Selective Baeyer-Villiger Oxidation of a-Fluorinated Ketones ; A New and Practical Route for the synthesis of a-Fluorinated Esters"Tetrahedron. 59. 1547-1552 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Mitsuhiro Kohda, Motoharu Seo, Kenji Uneyama: "A Novel Route to the Fluorinated Diimines : Carbon Monoxide-promoted Reductive Homocoupling of Fluorinated Imidoyl Iodides in the Presence of a Palladium Catalyst"Chem.Commun.. 1752-1753 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Fujiwara, Toshimasa, Katagiri, Kenji Uneyama: "Trifluoromethylated Amino alcohols as Chiral Ligands for Highly Enantioselective Reformatsky Reaction"Tetrahedron Lett.. 44. 6161-6163 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshihiro Yamauchi, Tomomi Kawa Hiromi Itahashi, Toshimasa Katagiri, Kenji Uneyama: "Generation and Reactions of a-Trifluoromethyl Stabilizaed Aziridinyl Aion ; a General Synthetic Precursor for Stereospecific Constnzction of α-amino-α-trifluoromethylated Quaternary Carbon"Tetrahedron Lett.. 44. 6319-6322 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Yutaka Ichihara, Takashi Nakagawa, Takeshi Kobayashi, Kenji Uneyama: "Unusual Reactions of N-allylic Difluoroenamines under Thermal Conditions"Chem.Commun.. 2902-2903 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takeshi Kobayashi, Takashi Nakagawa, Hideki Amii, Kenji Uneyama: "Mg-Promoted double Silylation of Trifluoroacetimidoyl Chlorides. A New Entry to the Fluorinated Dianion Equivalents"Org.Lett.. 5. 4297-4300 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshihiro Yamauchi, Tomomi Kawate, Toshimasa Katagiri, Kenji Uneyama: "Application of Trifluoromethyl Group Stabilizing Optically Active OxiranylandAziridinyl Anions for Stereospecific Syntheses of Trifluoromethylated Compounds"Tetrahedron. 59. 9839-9847 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hajime Abe, Hideki Amii, Kenji Uneyama: "Pd-catalyzed Asymmetric Hydrogenation of α-Fluorinated Iminoesters in fluorinated Alcoho : a New and Catalytic Enantioselective Synthesis of Fluoro α-amino Acid Derivative"Org.Lett.. 3. 313-315 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kenji Uneyama, Hironari Ohkura, Jinn Hao, Hideki Amii: "A Trial toward the Synthesis of γ-Fluorinated-β-amino-α-thioamino Acids. A finding of Desulfurizative C-C Bond formation in thio-Wittig Rearrangement of S-(N-Aryltrifluoroacetinvdoyl)thioglycolates."J.Org.Chem.. 66. 1026-1029 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Youshuke Kishikawa, Kenji Uneyama: "Rh(I)-catalyzed Coupling Cyclization of N-Aryl Trifluoroacetimidoyl Chlorides with alkynes : One-pot Synthesis of Fluorinated Quinolines."Org.Lett.. 3. 1009-1112 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshimasa Katagiri, Michiharu Handa, Yasuhisa Matsukawa, J.S.Dileep Kumar, Kenji Uneyama: "Efficient Synthesis of an Optically Pure β-Bromo-β,β-difluoroalanine Derivative, a General Precursor for b,b-Difluoroamino Acids."Tetrahedron : Asymmetry. 12. 1303-1311 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Takeshi Kobayashi, Hiroshi Terasawa, Kenji Uneyama: "Difluorinated Danishefsky's Dienes : a Vasatile C4 building Block for the Fluorinated 6-Membered ring."Org.Lett.. 3. 3103-3105 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshimasa Katagiri, Sachiko Yamaji, Michiharu Handa, Minoru Irie, Kenji Uneyama: "Diastereoselectivity Controlled by Electrostatic Repulsion between the Negative Charge on a Trifluoromethyl Group and that on Aromatic Rings."Chem.Commun.. 2054-2055 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshihiko Yamauchi, Toshimasa Katagiri, Kenji Uneyama: "The First Generation and Stereoselective Alkylation of α-Trifluoro-methyl Oxiranyl Anion."Org.Lett.. 4. 173-176 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masayuki Mae, Makoto Matsuwa, Hideki Amii, Kenji Uneyama: "A Facile Synthesis of Difluoromethylaziridines."Tetrahedron Lett.. 43. 2069-2072 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Horonari Ohkura, Michiharu Handa, Topshimasha Katagiri, Kenji Uneyama: "Diastereoselective Synthesis of S-tert-Butyl-β-(trifluoromethyl) isocysteine."J.Org.Chem.. 67. 2692-2695 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshimasa Katagiri, Yasuyuki Fujiwara, Satoshi Takahashi, Nobuyuki Ozaki, Kenji Uneyama: "Chiral Induction Controlled by aggregation of Organometallics ; Trifluoromethylated aminoalcohols for chiral Ligands Et2Zn Alkylation of Benzladehyde"Chem.Commun.. 986-987 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Vadim A.Soloshonok, Hironari Ohkura, Kenji Uneyama: "Biomimetic Reductive Amination of Perfluoroalkylcarboxylic Acids to α,α-Dihydroperfluoroalkylamines."Tetrahedron Lett.. 43. 5449-5452 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hiroshi Hata, Takeshi Kobayashi, Hideki Amii, Kenji Uneyama, John T.Welch: "A New Sequential Defluorination route to α-Fluoro-α,β-Unsaturated ketones from trifluoromethyl Ketones"Tetrahedron Lett.. 43. 5449-5452 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Satoru Kobayashi, Hiroaki Tanaka, Hideki Amii, Kenji Uneyama: "A New Finding in Selective Baeyer-Villiger Oxidation of a-Fluorinated Ketones ; A New and Practical Route-for the synthesis of a-Fluorinated Esters"Tetrahedron. 59. 1547-1552 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Mitsuhiro Kohda, Motoharu Seo, Kenji Uneyama: "A Novel Route to the Fluorinated Diimines : Carbon Monoxide-promoted Reductive Homocoupling of Fluorinated Imidoyl Iodides in the Presence of a Palladium Catalyst"Chem.Commun.. 1752-1753 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Fujiwara, Toshimasa, Katagiri, Kenji Uneyama: "Trifluoromethylated Amino alcohols as Chiral Ligands for Highly Enantioselective Reformatsky Reaction"Tetrahedron Lett.. 44. 6161-6163 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshihiro Yamauchi, Tomomi Kawate, Hiromi Itahashi, Toshimasa Katagiri, Kenji Uneyama: "Generation and Reactions of a-Trifluoromethyl Stabilizaed Aziridinyl Aion ; a General Synthetic Precursor for Stereospecific Construction of a-amino-α-trifluoromethylated Quaternary Carbon"Tetrahedron Lett.. 44. 6319-6322 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideki Amii, Yutaka Ichihara, Takashi Nakagawa, Takeshi Kobayashi, Kenji Uneyama: "Unusual Reactions of N-allylic Difluoroenamines under Thermal Conditions"Chem.Commun.. 2902-2903 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takeshi Kobayashi, Takashi Nakagawa, Hideki Amii, Kenji Uneyama: "Mg-Promoted double Silylation of Trifluoroacetimidoyl Chlorides. A New Entry to the Fluorinated Dianion Equivalents"Org.Lett.. 5. 4297-4300 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshihiro Yamauchi, Tomomi Kawate, Toshimasa Katagiri, Kenji Uneyama: "Application of Trifluoromethyl Group Stabilizing Optically Active Oxiranyland Aziridinyl Anions for Stereospecific Syntheses of Trifluoromethylated Compounds"Tetrahedron. 59. 9839-9847 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 藤原泰行, 片桐利真, 宇根山健治: "Trifluoromethylated amino alcohols as chiral ligands for highly enantioselective Reformatsky reaction"Tetrahedron Letters. 44. 6161-6163 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 山内禎啓, 川手朝海, 板橋宏美, 片桐利真, 宇根山健治: "Generation and reactions of α-trifluoromethyl stabilized aziridinyl anion, a general synthetic precursor for stereospecific construction of α-amino-α-trifluoromethylated quaternary carbon"Tetrahedron Letters. 44. 6319-6322 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 山内禎啓, 川手朝海, 片桐利真, 宇根山健治: "Trifluoromethyl-stabilized optically active oxiranyl and aziridinyl anions for stereospecific syntheses of trifluoromethylated compounds"Tetrahedron. 59. 9839-9847 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 小林 悟, 田中宏明, 網井秀樹, 宇根山健治: "A new finding in selective Baeyer-Villiger oxidation of -fluorinated ketones"Tetrahedron. 59. 1547-1552 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 小林武史, 中川貴司, 網井秀樹, 宇根山健治: "Mg-Promoted Double Silylation of Trifluoroacetimidoyl Chlorides. A New Entry to the Fluorinated Dianion Equivalents"Organic Letters. 5. 4297-4300 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 網井秀樹, 市原豊, 中川貴司, 小林武史, 宇根山健治: "Unusual Reactions of N-allylic Difluoroenamines under Thermal Conditions"Chemical Communication. 2902-2903 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Hata, T.Kobayashi, H.Amii, K.Uneyama, J.T.Welch: "A new sequential defluorination route to α-fluoro-α,β-unsaturated ketones from trifluoromethyl ketones"Tetrahedron Letters. 43. 6099-6102 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] V.A.Soloshonok, H.Ohkura, K.Uneyama: "Biomimetric reductive amiration of perfluoroalkyl-carboxylic acids to α,α-dihydroperfluoroalkylamines"Tetrahedron Letters. 43. 5449-5452 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Ohkura, M.Handa, T.Katagiri, K.Uneyama: "Diastereoselective synthesis of s-tert-butyle-β-(trifluoromethyl) isocysteine"Journal of Organic Chemistry. 67. 2692-2695 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Mae, M.Matsuura, H.Amii, K.Uneyama: "A facile synthesis of difluoromethylaziridines"Tetrahedron Letters. 43. 2069-2072 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Yamauchi, T.Katagiri, K.Uneyama: "The first generation and Stereospecific alkylation of α-trifluoromethyl oxiranyl anion"Organic Letters. 4. 173-176 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Uneyama, T.Katagiri, H.Amii: "New approaches to stereoselective synthesis of fluorinated Amino acids"有機合成化学協会誌. 60. 1069-1075 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Katagiri, M.Handa, Y.Matsukawa, T.S.Dilop Kumar, k.Uneyama: "Efficient synthesis of an optically pure β-bromo-β,β difluoroalanine derivative"Tetrahedron : Asymmetry. 12. 1303-1311 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Yamauchi, T.Katagiri, K.Uneyama: "The first Generation and Stereospecific Alkylation of α-Triflaoromethyl Oxiranyl Anion"Organic Letters. 4. 173-176 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2021-08-23  

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