Enantioselective Michael additions of nitromethane by a catalytic double activation method using chiral Lewis acid and achiral amine catalysts

被引:160
作者
Itoh, K
Kanemasa, S
机构
[1] Kyushu Univ, Inst Adv Mat Study, JST, CREST, Kasuga, Fukuoka 8168580, Japan
[2] Kyushu Univ, Grad Sch Engn Sci, Dept Mol & Mat Sci, Kasuga, Fukuoka 8168580, Japan
关键词
D O I
10.1021/ja027313+
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reactions of nitromethane with 1-(2-alkenoyl)-3,5-dimethylpyrazoles can be effectively catalyzed by R,R-DBFOX/Ph·Ni(ClO4)2·3H2O and achiral amine bases, each in a catalytic loading of 10 mol %, to give 1-(3-substituted 4-nitrobutanoyl)-3,5-dimethylpyrazoles in high chemical yields. Excellent enantioselectivities up to 98% ee have been achieved. The nitro moiety can be easily reduced on Raney nickel at atmospheric pressure, followed by concurrent cyclization, to give enantiomers of 4-substituted 2-pyrrolidinone derivatives after usual workup. This method can be successfully applied to a short step synthesis of (R)-(-)-rolipram. Copyright © 2002 American Chemical Society.
引用
收藏
页码:13394 / 13395
页数:2
相关论文
共 36 条
  • [1] Anada M, 1999, SYNLETT, P1775
  • [2] Chiral azacrown ethers derived from D-glucose as catalysts for enantioselective Michael addition
    Bako, P
    Kiss, T
    Toke, L
    [J]. TETRAHEDRON LETTERS, 1997, 38 (41) : 7259 - 7262
  • [3] D-glucose-based azacrown ethers with a phosphonoalkyl side chain:: application as enantioselective phase transfer catalysts
    Bakó, P
    Novák, T
    Ludányi, K
    Pete, B
    Toke, L
    Keglevich, G
    [J]. TETRAHEDRON-ASYMMETRY, 1999, 10 (12) : 2373 - 2380
  • [4] Bako P, 1997, SYNLETT, P291
  • [5] THE CRYSTAL-STRUCTURE, ABSOLUTE-CONFIGURATION, AND PHOSPHODIESTERASE INHIBITORY ACTIVITY OF (+)-1-(4-BROMOBENZYL)-4-(3-(CYCLOPENTYLOXY)-4-METHOXYPHENYL)-PYRROLIDIN-2-ONE
    BAURES, PW
    EGGLESTON, DS
    ERHARD, KF
    CIESLINSKI, LB
    TORPHY, TJ
    CHRISTENSEN, SB
    [J]. JOURNAL OF MEDICINAL CHEMISTRY, 1993, 36 (22) : 3274 - 3277
  • [6] ASYMMETRIC MICHAEL ADDITIONS CATALYZED BY NI(II) AND CO(II) COMPLEXES WITH HOMOCHIRAL LIGANDS
    BOTTEGHI, C
    PAGANELLI, S
    SCHIONATO, A
    BOGA, C
    FAVA, A
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1991, 66 (01): : 7 - 21
  • [7] BRAUN M, 1995, SYNLETT, P1174
  • [8] ASYMMETRIC INDUCTION IN BASE-CATALYZED MICHAEL ADDITION OF NITROMETHANE TO CHALCONE
    COLONNA, S
    HIEMSTRA, H
    WYNBERG, H
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1978, (06) : 238 - 239
  • [9] ASYMMETRIC INDUCTION IN THE MICHAEL REACTION BY MEANS OF CHIRAL PHASE-TRANSFER CATALYSTS DERIVED FROM CINCHONA AND EPHEDRA ALKALOIDS
    COLONNA, S
    RE, A
    WYNBERG, H
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1981, (02): : 547 - 552
  • [10] Diaz A, 1997, SYNTHESIS-STUTTGART, P559