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2003 Fiscal Year Final Research Report Summary

Liquid Crystal Control of uni-to multi-molecular Thermal Reactions

Research Project

Project/Area Number 13470496
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 医薬分子機能学
Research InstitutionKumamoto University

Principal Investigator

KUNIEDA Takehisa  Kumamoto University, Graduate School of Medical and Pharmaceutical Sciences, Professor, 大学院・医学薬学研究部, 教授 (80012649)

Co-Investigator(Kenkyū-buntansha) MATSUNAGA Hirofumi  Kumamoto University, Graduate School of Medical and Pharmaceutical Sciences, Research Associate, 大学院・医学薬学研究部, 助手 (10274713)
ISHIZUKA Tadao  Kumamoto University, Graduate School of Medical and Pharmaceutical Sciences, Associate Professor, 大学院・医学薬学研究部, 助教授 (60176203)
Project Period (FY) 2001 – 2003
KeywordsLiquid crystal / Smectic phase / cholesteric phase / Intramolecular cycloaddition / Intermolecular cycloaddition / Mitsunobu reaction / Orientation regulation
Research Abstract

The aim of this research is to establish the new methodology for highly orientation-regulated reaction system using liquid crystal as medium, with regularity and fluidity. The following typical reactions have tried with a variety of liquid crystal medium :
(1)Intramolecular [4+2] cycloaddition (unimolecular reaction) : Intramolecular uncatalyzed thermal cycloaddition reaction of trans-4-cyclohexylcyclohexyl decatrienoic acid esters in smectic liquid crystalline solvents such as bis(4-pentyloxyphenyl)trans-1,4-cyclohexanedicarboxylate (BPCD) was found to give bicyclic cycloadducts with extremely high diastereoselectivity and chemical yields, contrary to the poor results with isotropic medium such as 4-pentyloxyphenyl cyclohexanecarboxylate (PCC) and mesitylene.
(2)Intermolecular [4+2] cycloaddition (bimolecular reaction) : Moderate stereoselectivities and reaction accerelation effect were observed for intermolecular cycloaddition with pyrroles and allene diesters in smectic medium.
(3)Mitsunobu Reaction (tetramolecular reaction) : Unusual retention of the configuration of hydroxyl group of trans-4-substituted cyclohexanol by Mitsunobu reaction was observed in smectic medium, contrary to the usual result (inversion of configuration) in isotropic medium.

  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] Alaa A-M Abdel-Aziz, J.Okuno, S.Tanaka, T.Ishizuka, H.Matsunaga, T.Kunieda: "An unusual enhancement of chiral induction by chiral 2-imidazolidinone auxiliaries."Tetrahedron Letters. 41. 8533-8537 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Hoshimoto, H.Matsunaga, T.Kunieda: "Sterically Constrained 'Roofed' 2-Thiazolidinones as Excellent Chiral Auxiliaries."Chem.Pharm.Bull.. 48. 1541-1544 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 國枝武久: "複素五員環化合物を反応素子とする高度反応制御系の化学"薬学雑誌. 120. 1323-1335 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Morita, Y.Nagasawa, S.Yahiro, H.Matsunaga, T.Kunieda: "Versatile Synthons for Optically Pure α-Amino Aldehydes and α-Amino Acids : (+)- and (-)-4,5-Dialkoxy-2-oxazofidinones."Organic Letters. 3. 897-899 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Katahira, T.Ishizuka, H.Matsunaga, T.Kunieda: "Stereoselective intramolecular radical addition of polyhaloacyl pendant groups to the 1,3-dihydro-2-imidazolone moiety : the chiral synthesis of threo-diaminocarboxylic acids."Tetrahedron Letters. 42. 6319-6322 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] R.Seo, T.Ishizuka, Alaa.A-M Abdel-Aziz, T.Kunieda: "Versatile chiral synthons for 1,2-diamines : (4S,5S)- and (4R,5R)-4,5-dimethoxy-2-imidazoridinones."Tetrahedron Letters. 42. 6353-6355 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Alaa A-M Abdel-Aziz, H.Matsunaga, T.Kunieda: "Unusual N-acylation of sterically congested trans-4,5-disubstituted 2-midazolidinones : remarkably facile C-C bond formation."Tetrahedron Letters. 42. 6565-6567 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Matsunaga, N.Yoshioka, T.Kunieda: "Acceleration of ruthenium(II)- and rhodium(I)-catalyzed hydrogen-transfer reaction by rare earth metal triflates."Tetrahedron Letters. 42. 8857-8859 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Hoshimoto, H.Matsunaga, M.Wada, T.Kunieda: "Highly Accelerating Effect of Lewis Acids on Ruthenium(II)-catalyzed Radical Addition Reactions."Chem.Pharm.Bull.. 50. 435-438 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Isozumi, S.Hoshimoto, H.Matsunaga, T.Kunieda: "Chiral Functionalization of 2(3H)-Thiazolone. New Route to Chiral Synthons for 2-Amino Thiols."Heterocycles. 59. 323-332 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Alaa A-M Abdel-Aziz et al.: "An unusual enhancement of chiral induction by chiral 2-imidazolidinone auxiliaries"Tetrahedron Lett.. 41. 8533-5837 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Hoshimoto et al.: "Sterically Constrained 'Roofed' 2-Thiazolidinones as Excellent Chiral Auxiliaries"Chem.Pharm.Bull.. 48. 1541-1544 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kunieda: "Efficient Chiral Control Based on Five-Membered Heterocyclic and Related Systems"Yakugaku Zasshi. 120. 1323-1335 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Morita et al.: "Versatile Synthons for Optically Pure α-Amino Aldehydes and α-Amino Acids : (+)-and (-)-4,5-Dialkoxy-2-oxazolidinones"Org.Lett.. 3. 897-899 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Katahira et al.: "Stereoselective intramolecular radical addition of polyhaloacyl pendant groups to the 1,3-dihydro-2-imidazolone moiety : the chiral synthesis of threo-diaminocarboxylic acids"Tetrahedron Lett.. 42. 6319-6322 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] R.Seo et al.: "Versatile chiral synthons for 1,2-diamines : (4S,5S)-and (4R,5R)-4,5-dimethoxy-2-imidazoridinones"Tetrahedron Lett.. 42. 6353-6355 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Alaa A-M Abdel-Aziz et al.: "Unusual N-acylation of sterically congested trans-4,5-disubstituted 2-imidazolidinones : remarkably facile C-C bond formation"Tetrahedron Lett.. 42. 6565-6567 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Matsunaga et al.: "Acceleration of ruthenium(II)-and rhodium(I)-catalyzed hydrogen-transfer reaction by rare earth metal triflates"Tetrahedron Lett.. 42. 8857-8859 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Hoshimoto et al.: "Highly Accelerating Effect of Lewis Acids on Ruthenium(II)-catalyzed Radical Addition Reactions"Chem.Pharm.Bull.. 50. 435-438 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Isozumi et al.: "Chiral Functionalization of 2(3H)-Thiazolone. New Route to Chiral Synthons for 2-Amino Thiols"Heterocycles. 59. 323-332 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kunieda et al.: "Part B, Chapter 5. Synthesis and Reaction of 2(3H)-Oxazolones and 2(5H)-Oxazolones. Chemistry of Heterocyctic Compounds, (ed. by David C. Palmer) New York, 2004."John Wiley & Sons, Inc.. (2004)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2005-04-19  

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