ASYMMETRIC MICHAEL REACTION OF ALPHA-CYANO CARBOXYLATES CATALYZED BY A RHODIUM COMPLEX WITH TRANS-CHELATING CHIRAL DIPHOSPHINE PHTRAP

被引:99
作者
SAWAMURA, M [1 ]
HAMASHIMA, H [1 ]
ITO, Y [1 ]
机构
[1] KYOTO UNIV,FAC ENGN,DEPT SYNTHET CHEM & BIOL CHEM,KYOTO 60601,JAPAN
关键词
D O I
10.1016/S0040-4020(01)89377-7
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Asymmetric Michael reaction of 2-cyanopropionates with vinyl ketones or acrolein in the presence of 0.1-1 mol% of a rhodium catalyst prepared in situ from RhH(CO)(PPh(3))(3) and a trans-chelating chiral diphosphine ligand (S,S)-(R,R)-PhTRAP in benzene at 3-5 degrees C gave optically active Michael adducts with high enantiomeric excesses (83-93% ee) in high yields. The reaction of 2-cyanopropionate with methacrolein and crotonaldehyde proceeded somewhat slowly, giving diastereomer mixtures in moderate enantioselectivities but in low diastereoselectivities. The reaction of 2-cyanobutyrate and 2-cyano-3-methylbutyrate with acrolein gave corresponding Michael adducts with much lower enantiomeric excesses than that of 2-cyanopropionates. The Michael addition product from acrolein was converted into an optically active alpha-methyl-alpha-amino acid.
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页码:4439 / 4454
页数:16
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