The complete characterization of a rhodium Lewis acid-dipolarophile complex as an intermediate for the enantioselective catalytic 1,3-dipolar cycloaddition of C,N-diphenylnitrone to methacrolein

被引：81
作者：
Carmona, D [1 ]
Lamata, MP
Viguri, F
Rodríguez, R
Oro, LA
Balana, AI
Lahoz, FJ
Tejero, T
Merino, P
Franco, S
Montesa, I
机构：
[1] Univ Zaragoza, Dept Quim Inorgan, Consejo Super Invest Cient, Inst Ciencia Mat Aragon, E-50009 Zaragoza, Spain
[2] Univ Zaragoza, Dept Quim Organ, Consejo Super Invest Cient, Inst Ciencia Mat Aragon, E-50009 Zaragoza, Spain
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 09期
关键词：
D O I：
10.1021/ja031995z
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The 1,3-dipolar cycloaddition reaction of C,N-diphenylnitrone with methacrolein is efficiently catalyzed by the rhodium diphosphine compound (SRh,RC)-[(η5-C5Me5)Rh(R-Prophos)(H2O)](SbF6)2 [R-Prophos = (R)-(+)-1,2-bis(diphenylphosphino)-propane, 1·SbF6]; the asymmetric catalytic process occurs with reversal of regioselectivity, perfect endo selectivity, and up to 92% ee. The complete (NMR and X-ray analysis) characterization of the involved intermediate (SRh,RC)-[(η5-C5Me5)Rh(R-Prophos)(methacrolein)](SbF6)2 (7·SbF6) allows us to interpret the observed selectivity. Copyright © 2004 American Chemical Society.
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页码：2716 / 2717
页数：2
相关论文
共 14 条
  • [1] Chiral rhodium complexes as catalysts in Diels-Alder reactions
    Carmona, D
    Cativiela, C
    GarciaCorreas, R
    Lahoz, FJ
    Lamata, MP
    Lopez, JA
    deViu, MPLR
    Oro, LA
    SanJose, E
    Viguri, F
    [J]. CHEMICAL COMMUNICATIONS, 1996, (10) : 1247 - 1248
  • [2] Chiral ruthenium complexes as catalysts in enantioselective Diels-Alder reactions. Crystal structure of the Lewis acid dienophile adduct
    Carmona, D
    Cativiela, C
    Elipe, S
    Lahoz, FJ
    Lamata, MP
    Pilar, M
    de Viu, LR
    Oro, LA
    Vega, C
    Viguri, F
    [J]. CHEMICAL COMMUNICATIONS, 1997, (24) : 2351 - 2352
  • [3] Arene ruthenium complexes with pyridyloxazolines: synthesis and applications as asymmetric catalysts for Diels-Alder reactions
    Davenport, AJ
    Davies, DL
    Fawcett, J
    Garratt, SA
    Russell, DR
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (23): : 4432 - 4441
  • [4] C-2-SYMMETRIC CATIONIC COPPER(II) COMPLEXES AS CHIRAL LEWIS-ACIDS - COUNTERION EFFECTS IN THE ENANTIOSELECTIVE DIELS-ALDER REACTION
    EVANS, DA
    MURRY, JA
    VONMATT, P
    NORCROSS, RD
    MILLER, SJ
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (07): : 798 - 800
  • [5] Optically active isoxazolidines via asymmetric cycloaddition reactions of nitrones with alkenes: Applications in organic synthesis
    Frederickson, M
    [J]. TETRAHEDRON, 1997, 53 (02) : 403 - 425
  • [6] Gothelf KV, 2002, CYCLOADDITION REACTIONS IN ORGANIC SYNTHESIS, P211
  • [7] Asymmetric 1,3-dipolar cycloaddition reactions
    Gothelf, KV
    Jorgensen, KA
    [J]. CHEMICAL REVIEWS, 1998, 98 (02) : 863 - 909
  • [8] Catalytic enantioselective 1,3-dipolar cycloaddition reactions of nitrones
    Gothelf, KV
    Jorgensen, KA
    [J]. CHEMICAL COMMUNICATIONS, 2000, (16) : 1449 - 1458
  • [9] Kanemasa S, 2002, CYCLOADDITION REACTIONS IN ORGANIC SYNTHESIS, P249
  • [10] Kündig EP, 1999, ANGEW CHEM INT EDIT, V38, P1220
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