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CHIRAL TRIOLS OF C3-SYMMETRY: SYNTHESIS AND APPLICATION TO CHIRAL RECOGNITION

Research Project

Project/Area Number 13640533
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKyoto Institute of Technology

Principal Investigator

AMIKO Atsushi  KYOTO INSTITUTE OF TECHNOLOGY, GRADUATE SCHOOL OF ENGINEERING, ASSOCIATE PROFESSOR, 工芸科学研究科, 助教授 (30184203)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2003: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2002: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2001: ¥1,200,000 (Direct Cost: ¥1,200,000)
Keywordsdouble aldol reaction / boron-mediated albol reaction / carboxylic ester / asymmetric synthesis / chiral triol of C3-symmetry / chiral synthon / doubly borylated enolate / carbon-bound enolate / chiral recognition / 分子不斉 / 金属錯体 / 炭素結合エノレート
Research Abstract

We have devised new asymmetric boron-mediated double aldol reactions complementarily useful for the synthesis of aliphatic and aromatic substituted chiral triols of C3-symmetry, which are potential precursors for the study of asymmetric catalysis and chiral recognition, via double aldol reactions of a chiral acetate ester or a chiral acetyloxazolidinone.
Chiral dendrimenrs having a chiral triol of C3-symmetry as a core element with 3, 5-disubstituted benzyl ether type dendrone of the 3^<rd> to 5^<th> generation were synthesized. The chiroptical properties of these dendrimers were examined and shown to exibhit the "dilution effect", eveidence of their of "molecular chirality being not observed.
Tris-pyridine, and tris-bipyridine substituted compounds were synthesized to examine properties of their metal complexes. Tris-2-pyridylmethyl and tris-3-pyridylmethl substituted chiral triols were synthesized. Their copper complexes were shown to be 1: 1, and 2: 1 complex, respectively, by ESI-MS measurement. Catalytic of these complexes was examined.
Tris-6'-methyl-6-(2, 2 -bipyridylmethyl) substituted triols did not afford Ru complex upon treatment with 5'-methyl-5-chloromethy-2, 2'bipyridine proceeded only low yield (<10%). An alternate route using Stille coupling of stannylpyridine and 2-bromopyridylmethyl substituted chiral triols will be executed.

Report

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

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Abiko, A.: "The first doubly borylated enolate as an intermediate of double aldol reaction"J.Am.Chem.Soc.. 123. 4605-4606 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Abiko, A: "Mechanism of the Double Aldol Reaction : The First Spectroscopic Characterization of a Carbon-bound Boron Enolate derives from Carboxylic Esters"J.Am.Chem Soc.. 124. 10759-10764 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Inoue, T.: "Boron-Mediated Aldol Reaction of Carboxylic Esters : Complementary Anti- and Syn-Selective Asymmetric Aldol Reactions"J.Org.Chem.. 67. 5250-5256 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Furuno, H.: "The Asymmetric Double Aldol Reaction of Acyl-oxazolidinone"Tetrahedron Letters. 46・48. 8297-8299 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 安孫子 淳: "カルボン酸エステルのボロンアルドール反応"有機合成化学協会誌. 61・1. 24-34 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Abiko, A: "The Boron-Mediated Aldol Reaction of Carboxylic Esters"Acc.of Chem.Res.. (印刷中). (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Abiko, T.Inoue, H.Schwalbe, C.Fieres, S.Masamune: "T The First Doubly Borylated Enolate as an Intermediate of the Double Aldol Reaction"J. AM. Chem. Soc.. 123,(19). 4605-4606 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Abiko, T.Inoue, MMasamune: "Mechanism of the Double Albol Reaction: The first Spectroscopic Charaterization of a Carbon-bound Boron Enolate derives from Carboxylic Esters"J. Am. Chem. Soc.. 124. 10759-10764 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Inoue, J.-F.Liu, D.C.Buske, A.Abiko: "Boron-Mediated Aldol Reaction of Carboxylic Esters: Complementary Anti-and Syn-Selective Asymmetric Aldol Reactions"J. Org. Chem.. 67. 5250-5256 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Furuno, T.Inoue, A.Abiko: "The Asymmetric Double Reaction of Acyloxazolidinone"Tetrahedron Letters. 46. 8297-8299 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Abiko: "Boron-mediated aldol reaction of carboxylic esters"J. Syn. Org. Chem. Soc.. 61(1). 24-34 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Abiko: "Boron-mediated aldol reaction of carboxylic esters"Acc. Chem, Res.. (in press). (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 安孫子 淳: "カルボン酸エステルのボロンアルドール反応"有機合成化学協会誌. 61. 24-34 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Abiko, A.: "The Boron-Mediated Aldol Reaction of Carboxylic Esters"Acc.Chem.Research. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Abiko, A.: "Mechanism of the Double Aldol Reaction : The First Spectroscopic Characterization of a Carbon-bound Boron Enolate derives from Carboxylic Esters"J. Am. Chem. Soc.. 124. 10759 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Abiko, A.: "Boron-Mediated Aldol Reaction of Carboxylic Esters : Complementary Anti-and Syn-Selective Asymmetric Aldol Reactions"J. Org. Chem.. 67. 5250 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Abiko, A.: "The Asymmetric Double Aldol Reaction of Acyl-oxazolidinone"Tetrahedron Letters. 46. 8297 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Abiko, A: "Dicyclohexylboron trifluoromethanesulfonate"Organic Synthesis. 79. 103 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Abiko, A: "2-(N-Benzyl-N-mesitylenesulfonyl)amino-1-phenyl-1-propyl propionate"Organic Synthesis. 79. 109 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Abiko, A: "Anti-selective boron-mediated asymmetric aldol reaction of carboxylic esters"Organic Synthesis. 79. 115 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Abiko, A: "The first doubly borylated enolate as an intermediate of double aldol reaction"J.Am.Chem.Soc.. 123. 4605 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Abiko, A: "Dicyclohexylboron trifluoromethanesulfonate"Organic Synthesis. 79(印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Abiko, A: "2-(N-Benzyl-N-mesitylenesulfbnyl)amino-1-phenyl-1-propyl propionate"Organic Synthesis. 79(印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Abiko, A: "Anti-selective boron-mediated asymmetric aldol reaction of carboxylic esters"Organic Synthesis. 79(印刷中). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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