| 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, Assistant Professor, 大学院・医学薬学研究部, 助教授 (60176203)
ARITA Masafumi Mitsubishi Pharma Corporation, Pharmaceutical Research Unit, Chief, 研究部長
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| Research Abstract |
The aim of this research is to establish the methodology for i)simple preparation of tricyclic "roofed" 2-oxazolidinones, 2-imidazolidinones and 2-thiazolidinones with comformational rigidity and steric congestion as extremely powerful chiral auxiliaries by catalytic resolution, and ii)excellent asymmetric reactions with bicyclic 2-amino alcohols, 1,2-diamines and 2-aminothiols derived from the above tricyclic compounds and their derivatives.
(1)Easy access to highly efficient chiral auxiliaries by kinetic resolution
The optically active "roofed" 2-oxazolidinones, 2-imidazolidinones and 2-thiazolidinones 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 ligands
Bicyclic "roofed" 2-amino alcohols, 1,2-diamines and 2-aminothiols derived from the corresponding tricyclic compounds have been proven to be good to excellent chiral ligands for following metal-catalyzed asymmetric reactions :
i)"2-Aminoalcohol" ligands :
a)asymmetric borane reduction of ketones with oxazaborolidine-borane system.
b)Practical synthesis of versatile chiral synthons, 4,5-dimethoxy-2-oxazolidinone and 4,5-demethoxy-2-imidazolidinone.
c)asymmetric aldol reaction with Cu(II) catalyst.
ii)"cis-1,2-Diamine" ligands :
a)Ruthenium (II)-catalyzed asymmetric transfer hydrogenation of ketones.
iii)"2-Aminothiol" ligands:
a)Pd (II)-catalyzed asymmetric alkylation of allylacetates.
b)Cu (II)-catalyzed asymmetric Diels-Alder reaction.
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