2003 Fiscal Year Final Research Report Summary
Liquid Crystal Control of uni-to multi-molecular Thermal Reactions
| Project/Area Number |
13470496
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
医薬分子機能学
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| Research Institution | Kumamoto University |
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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)
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| 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)
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| Project Period (FY) |
2001 – 2003
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| Keywords | Liquid crystal / Smectic phase / cholesteric phase / Intramolecular cycloaddition / Intermolecular cycloaddition / Mitsunobu reaction / Orientation regulation |
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| 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.
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