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Study on chiral discrimination mechanism upon crystallization and its application to development of novel general optical resolution method.

Research Project

Project/Area Number 09450330
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionThe University of Tokyo

Principal Investigator

SAIGO Kazuhiko  The University of Tokyo, Graduate School of Frontier Sciences, Professor, 大学院・新領域創成科学研究科, 教授 (80016154)

Project Period (FY) 1997 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 2000: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1999: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 1998: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1997: ¥3,600,000 (Direct Cost: ¥3,600,000)
KeywordsOptical Resolution / Diastereomeric Method / Crystal Engineering / Hyrogen Bond / ジアステレオマ-塩法
Research Abstract

In order to clarify the mechanism of optical resolution upon crystallization and to rationally design a tailor-made resolving agent, the optical resolution of systematically selected racemates with series of resolving agents have been studied. As a result of comparison of the crystal structures between the less- and more-soluble diastereomeric salts, it has been found that the lesssoluble salts were effectively stabilized by hydrogen-bonding, CH…π, and van der Waals interactions. On the basis of this result, we desinged 2-naphthylglycolic acid, cis-1-amino-2-indanol, etc., in which a hydrogen-bonding group and other interacting group (s) were suitably placed to stabilize the less-soluble salts. In fact, these resolving agents had excellent resolution ability for 1-arylethylamines and 2-arylalkantoic acids, respectively. Thus, we have succeeded in designing novel resolving agents on the basis of the concept of crystal engineering.
On the other hand, we focused on the fact that there is a similarity in crystal structure between a conglomerate salt of a chiral amine with an achiral carboxylic acid and a less-soluble diastereomeric salt which crystallizes exclusively during optical resolution. Then, we checked the crystal structures of the salts of racemic amine with racemic carboxylic acid, in which one of the enantiopure components is a good resolving agent for the other component. As a result, it was found that conglomerate tends to be formed in extremely high probability in such a system.

Report

(5 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (53 results)

All Other

All Publications (53 results)

  • [Publications] A.Sudo ら: "cis-2-Amino-3,3-dinethyl-1-indanol : Application as a Highly Efficient Chiral Anxiliary for the Diels-Alder Reaofish"Chem.Lett.. 97-98 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Hayashi ら: "Synthesis of a New Chiral (β-Aminoalkyl) phosphine Ligand and Its Application to a Catalytic Asymnetric Grighard Cross-Compling Reaction"Enantioner. 2. 293-296 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Sudo ら: "An efficient phosphorons-containing oxazoline ligand derived from cis-2-amino-3,3-dinethyl-1-indanol : application to the rhodium-catalyzed enantiaselective hydrosilylation of Ketones"Tetrahedron : Asymmetry. 8. 3205-3208 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Sakai ら: "Reciprocal Resolution of 1-(4-nethylpheryl) ethylamine and 2-Hydroxy-4-phenylbutyric Acid, and Habit Modification of a Less-Soluble Diatereoneric Solt with a Chiral Additive"Enantioner. 3. 23-35 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara ら: "Systematic Study of Chiral discrimination upon crystallization part2.Chiral discrimination of 2-arylalkanoic acids by (1R,2S)-2-amino-1,2-diphenylethanol"J.Chen.Soc.Perkin Trans.2. 1767-1775 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] H.Kagoshima ら: "An Activated Germanium Metal-Promoted, Higly Diastereoselective Reformatsky Reactior"J.ORg.Chem.. 63. 691-697 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Mstsui ら: "Application of erythro-2-Amino-1,2-diphenylethanol as a Highly Efficient Chiral Auxiliary.Highly Stereoselective Standinger-type β-Lactam Synthesis Using a 2-Chloro-1 metylpyridinin salt"Synthesis. 1161-1166 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara ら: "(2-Naphthyl)glycolic acid : a tailored resolving agent for p-substituted 1-arylalkylamines"Tetrahedron : Asymmetry. 9. 2219-2222 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kohara ら: "Design, Synthesis, and Optical Resolution of a Novel Non-Natural Auxiliang,1-(2,5-Dimethoxyphenyl) ethylamine Application to Diastereoselective Alkylation of Aldimines"Tetrahedron. 55. 6453-6464 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kohara ら: "A new-non-natural chiral auxiliary : design, synthesis, and resolution of 1-mesityl ethylamine and its application in the asymmetric a2a-Diels-Alder reaction"Tetrahedron : Asymmetry. 10. 4831-4840 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Matsui ら: "Application of cis-2-Amino-3,3-dimethyl-1-indanol as an Efficient chiral Auxiliary to the Asymmetric Ireland-Claisen Reagrangement"Enautimer. 5. 105-108 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Hashimoto ら: "Stereoselective Synthesis of Opticaly-Active β-1-actams by the Reaction of Chiral Imines Derived from erythro-2-Amino-1,2-diphenylethanol with Ester Enolates"Heterocycles. 52. 1001-1004 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara ら: "Chiral discrimination of 2-arylalkanoic acids by (1S,2R)-1-aminoindan-2-ol through the formation of a consistent columnar hydrogen-bond network"J.Chem.Soc., Perkin Trans.2. 111-119 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara ら: "A High Performance, tailor-made Mesolving agent : remarkable enhancement of resdution ability by Introducing a naphthylgroup into the fundamental Skeletion"J.Chen.Soc., Perkin Trans.2. 1339-1347 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kohara ら: "Palladium-Catalyzed Allylic Alkylation Using a Novel Chiral Omino-Phosphine Ligand Derived from 1-Mesityletrylamine"Synleft. 517-519 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara ら: "Effect of a Substitment or an Aromatic Group in Diastereomeric Resolution"Tetrahedron. 56. 6651-6658 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Hashimoto ら: "An efficient Phosphorary-Containing oxazoline ligand derived from cis-2-amino-3,3-demethyl-1-indanol : application to the palladium catalyzed asymmetric Heck reaction"Tetrahedron : Asymmetry. 11. 2205-2210 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 西郷和彦: "光学分割法"廣川書店. (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbana ら: "Topics in Stereochemistus"(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Sudo, K.Saigo: "cis-2-Amino-3, 3-dimethyl-1-indanol : Application as a Highly Efficient Chiral Auxiliary for the Diels-Alder Reaction"Chem.Lett.. 97-98 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Hayashi, K.Takaoki, Y.Hashimoto, K.Saigo: "Synthesis of a New Chiral (β-Aminoalkyl) phosphine Ligand and Its Application to a Catalytic Asymmetric Grignard Cross-Coupling Reaction"Enantiomer. 2. 293-296 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Sudo, H.Yoshida, K.Saigo: "An efficient phosphorous-containing oxazoling ligand derived from cis-2-amino-3, 3-dimethyl-1-indanol : application to the rhodium-catalyzed enantioselective hydrosilylation of ketones"Tetrahedron : Asymmetry. 8. 3205-3208 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Sakai, S.Yoshida, Y.Hashimoto, K.Kinbara, K.Saigo, H.Nohira: "Reciprocal Resolution of 1-(4-Methylphenyl) ethylamine and 2-Hydroxy-4-phenylbutyric Acid, and Habit Modification of a Less-Soluble Diastereomeric Salt with a Chiral Additive"Enantiomer. 3. 23-35 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara, Y.Kobayashi, K.Saigo: "Systematic study of chiral discrimination upon crystallization. Part 2. Chiral discrimination of 2-arylalkanoic acids by (1R, 2S)-2-amino-1, 2-diphenylethanol"J.Chem.Soc., Perkin Trans.. 2. 1767-1775 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] H.Kagoshima, Y.Hashimoto, D.Oguro, K.Saigo: "An Activated Germanium Metal-Promoted, Highly Diastereoselective Reformatsky Reaction"J.Org.Chem.. 63. 691-697 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Matsui, Y.Hashimoto, K.Saigo: "Application of erythro-2-Amino-1, 2-diphenylethanol as a Highly Efficient Chiral Auxiliary. Highly Stereoselective Staudinger-Type β-Lactam Synthesis Using a 2-Chloro-1-methylpyridinium Salt as a Dehydrating Agent"Synthesis. 1161-1166 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara, Y.Harada, K.Saigo: "(2-Naphthyl) glycolic acid : a tailored resolving agent for p-substituted 1-arylethylamines"Tetrahedron : Asymmetry. 9. 2219-2222 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kohara, Y.Hashimoto, K.Saigo: "Design, Synthesis, and Optical Resolution of a Novel Non-natural Auxiliary, 1-(2, 5-Dimethoxyphenyl) ethylamine. Application to Diastereoselective Alkylation of Aldimines"Tetrahedron. 55. 6453-6464 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kohara, Y.Hashimoto, R.Shioya, K.Saigo: "A new non-natural chiral auxiliary : design, synthesis, and resolution of 1-mesitylethylamine and its application in the asymmetric aza-Diels-Alder reaction"Tetrahedron : Asymmetry. 10. 4831-4840 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Matsui, N.Oka, Y.Hashimoto, K.Saigo: "Application of cis-2-Amino-3, 3-dimethyl-1-indanol as an Efficient Chiral Auxiliary to the Asymmetric Ireland-Claisen Reaarangement. Improvement of the Diastereoselectivity by Combinational Use of Chlorodimethylsilane as a Silylating Agent"Enantiomer. 5. 105-108 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Hashimoto, T.Ogasawara, M.Hayashi, K.Saigo: "Stereoselective Synthesis of Optically Active β-Lactams by the Reaction of Chiral Imines Derived from erythro-2-Amino-1, 2-diphenylethanol with Ester Enolates"Heterocycles. 52. 1001-1004 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara, Y.Kobayashi, K.Saigo: "Chiral discrimination of 2-arylalkanoic acids by (1S, 2R)-1-aminoindan-2-ol through the formation of a consistent columnar supramolecular hydrogen-bond network"J.Chem.Soc., Perkin Trans. 2. 111-119 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara, Y.Harada, K.Saigo: "A high-performance, tailor-made resolving agent : remarkable enhancement of resolution ability by introducing a naphthyl group into the fundamental skeleton"J.Chem.Soc., Perkin Trans. 2. 1339-1347 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kohara, Y.Hashimoto, K.Saigo: "Palladium-Catalyzed Allylic Alkylation Using a Novel Chiral Imino-Phosphine Ligand Derived from 1-Mesitylethylamine"Synlett.. 517-519 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kinbara, K.Oishi, Y.Harada, K.Saigo: "Effect of a Substituent on an Aromatic Group in Diastereomeric Resolution"Tetrahedron. 56. 6651-6655 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Hashimoto, Y.Horie, M.Hayashi, K.Saigo: "An efficient phosphorous-containing oxazoline ligand derived from cis-2-amino-3, 3-dimethyl-1-indanol : application to the palladium-catalyzed asymmetric Heck reaction"Tetrahedron : Asymmetry. 11. 2205-2210 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Hashimoto ら: "Stereoselective synthesis of optically active B-lactams by the reaction at chiral imines derived from erythro-2-amino-1,2-diphenylethanol with ester endates"Heterocycles. 52. 1007-1004 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Kohara ら: "Palladium-Catalyzed Allylic Alkylation Using a Novel Chiral Imino Phosphine Ligand Derived from 1-Mesitylethylamine"Synletre. 517-519 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Hashimoto ら: "An efficient phosphorous-containing oxazoline ligand derived from cis-2-amino-3,3-dimethyl-1-indanol-application to the palladium catalyzed"Tetrahednsn : Asymmetry. 11. 2205-2210 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Matsui ら: "Application of cis-2-amino-3,3-dimethyl-1-indanol as an efficient chiral auxiliary to the asymmetric Ireland-Claisen rearrangement. Improvement of the diastereoselectivity by combinational use of chlorodimethylsilane as a silylating agent"Enantiomer. 5. 105-108 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kirbana ら: "A high-performance, tailor-made resolving agent : remarkable enhancement of resolution ability by introducing a naphthyl group to the fundamental skeleton"Journal of the Chemical Society, Perkin Transactions 2. 1339-1347 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T. Kohara ら: "Design, Synthesis, and Optical Resolution of a Novel Non-natural Chiral Auxiliary, 1-(2,5-Dimethoxyphenyl)ethylamine. Application to Diastereomerective Alkylation on of Aldimines"Tetrahedron. 55. 6453-6464 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Kohara ら: "A new non-natural chiral auxiliary ; design, synthesis and resolution of 1-nesityl ethylamine and its application in the asymnetric aza-Diels-Alder reaction"Tetrahedron : Asymmethy. 10. 4831-4840 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Kinbara ら: "Chiral Discrimination of 2-arylalkanoic acids by (1S,2R)-1-amino-2-indonol through the formation of a consistent columu*nar hydrogen-bond network"Journal of the Chemical Socity, Derkin Ttansactins 2. 111-119 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Kinbara ら: "Effect of a substituent on an Aromatic Gronp in Diastereomeric Resolution"Tetrahedron. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] H.Kagoshima ら: "An Activoted Germanium Metal-Pronoted, Highly Diastereoselective Reformatsky Reaction" The Journal of Organic Chemistry. 63. 691-697 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 西郷 和彦ら: "非天然型不斉助剤を用いる不斉合成反応の開発" 有機合成化学協会誌. 56. 386-394 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Hayashi ら: "A Novel optically active bisohosohine ligand CDP, derived from an anti head-to-head conmarin dimer : synthesis and application to the rhodium-catalyzed osymmetric hydroganation of arylenamides" Tetrahedron : Asymmetry. 9. 1863-1866 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Sakaiら: "Reciprocal Resalution of 1- (4-Methylpheryl) ethylamine and 2-Hydroxy-4-phenylbutyric Acid, and Habit Modification of a Less-soluble Diastoeomeric Salt with a Chiral Additive" Enantiomer. 3. 23-35 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Kinharaら: "(2-Naphthyl) glycolicacid : a tailored resolving agent for p-suostituted l-arylethylamines" Tetrahedron : Asymmetry. 9. 2219-2222 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Matsui ら: "Application of erythro-2-Amino-1,2-dipherylethanol as a Highry Efficient Chiral Auxiliary. Highly Stereoselective Staudinger-Type B-lactam Smthesis Using a 2-Chloro-1-methclpyridinim Salt." Synthesis. 1161-1166 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Kinbaraら: "Systematic study of chiral discrimination upon crystallization. Part2.Chinal discrimination of 2-arylalkanoic acids by (1R,2S) -2-amino-1,2-diphenxlethanol" Journal of the Chemical Society, Perkin Tramsaction 2. 1767-1775 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 西郷 和彦(柴崎正勝編): "創薬化学の基礎となる不斉反応 I" 廣川書店, 289 (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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