| Project/Area Number |
10470471
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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 |
Chemical pharmacy
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| Research Institution | Kumamoto University |
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Principal Investigator |
KUNIEDA Takehisa Kumamoto Univ., Fac.Pharm.Sci, Professor, 薬学部, 教授 (80012649)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUNAGA Hirofumi Kumamoto Univ., Fac.Pharm.Sci, Research Associate, 薬学部, 助手 (10274713)
ISHIZUKA Tadao Kumamoto Univ., Fac.Pharm.Sci, Associate Professor, 薬学部, 助教授 (60176203)
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| Project Period (FY) |
1998 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥11,600,000 (Direct Cost: ¥11,600,000)
Fiscal Year 2000: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1999: ¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 1998: ¥5,500,000 (Direct Cost: ¥5,500,000)
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| Keywords | 2-Oxazolone / 2-Imidazolone / 2-Oxazolidinone / 2-Imidazolidinone / Chiral Auxiliaries / Chiral Ligands / Kinetic Resolution / Bis(oxazoline) ligand / オキサザボロリジン / メソ体 / 不斉モノ脱アシル化 |
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| Research Abstract |
The aim of this research is to establish the methodology for i) simple preparation of tricyclic 2-oxazolidinones and 2-imidazolidinones with conformational rigidity and steric congestion as extremely powerful chiral auxiliaries by catalytic resolution, and ii) excellent asymmetric reactions with bicyclic 2-amino alcohols and 1,2-diamines derived from the above tricyclic compounds.
1. Easy access to highly efficient chiral auxiliaries by kinetic resolution :
The optically active "roofed" 2-oxazolidinones and 2-imidazolidinones were readily obtained from kinetic resolution with oxazaborolidine catalysts, which is an alternative method for optical resolution with "MAC-acid" (2-exo-methoxy-1-apocamphanecarboxylic acid).
2. Development of highly efficient chiral auxiliaries :
Diastereoselectivity which is induced by the use of 2-imidazolidinone auxiliaries is greatly dependent on the N-substituents of the heterocycles, among which the bulky arenesulfonyl group is the moiety of choice. Reactions of this type afford an excellent level of diastereoselection in the methylation of N'-butyryl-2-imidazolidinones via the metal enolates.
3. Development of highly efficient chiral amino alcohols :
(1) chiral ligands : The chiral cis-2-aminoalcohols derived from ring-opening of the above tricyclic 2-oxazolidinones played a promising role in performing the high level of catalytic chiral discrimination (asymmetrization of meso-1,3-diacetyl-2-imidazolidinones).
(2) chiral reactants : The alkoxide of the sterically congested 2-aminoalcohols served well as chiral discriminating agents for highly efficient dissymmetrization of meso-1,3-diacetyl-2-imidazolidinones.
(3) C_2-symmetrical bis (oxazoline) ligands : The use of sterically congested C_2-symmetrical bis (oxazoline) ligands derived from the above amino alcohols provided the unexpected enantioselection for aldol reactions catalyzed by the Cu (II) complexes, which was an important findings for a design of new chiral synthetic processes.
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