「アミン類の不斉触媒合成」
(Asymmetric Reactions for Amines)

Kiyoshi Tomioka
Graduate School of Pharmaceutical Sciences
Kyoto University

 Asymmetric approach to chiral amines provides a challenge to organic chemistry. A carbon-carbon bond forming approach (a) with an imine carbon-nitroge double bond led us to the discovery of (1) Mannich-type reaction of three-component reagent of a lithium enolate involving a chiral ligand for lithium,1 (2) chiral amidophosphane-copper(II)-catalyzed addition reaction of dialkylzinc reagents,2 and (3) chiral amidophosphane-rhodium(I)-catalyzed addition reaction of arylboron reagents.3


 A nitrogen-carbon bond forming approach (b) with an olefin carbon-carbon double bond provided us (1) the asymmetric Michael reaction of a lithium amide-complexed with a chiral diether with an electron-withdrawing group-activated double bond4 and (2) catalytic asymmetric intramolecular hydroamination of a lithium amide-complexed with Bisoxazoline ligand with a simple olefin.5

References
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3. J. Am. Chem. Soc. 2004, 126, 8128. Pure Appl. Chem. 2006, 78, 2029.
4. J. Am. Chem. Soc. 2003, 125, 2886. Chem. Commun. 2004, 1850. Tetrahedron Lett. 2004, 45, 9261 J. Org. Chem. 2006,     71, 4706. Tetrahedron 2006, 62, 8351.
5. Tetrahedron Lett. 2007, 0000.