'Metal ion electrophilic catalysis' in ring-opening reactions of 1,2-epoxides by metal halides in ionic liquids

被引：11
作者：
Betti, Cecilia
Landini, Dario
Maia, Angelamaria
机构：
[1] Univ Milan, Dipartimento Chim Organ & Ind, I-20133 Milan, Italy
[2] Ist CNR, ISTM, I-20133 Milan, Italy
来源：
SYNLETT | 2006年 / 09期
关键词：
epoxides; vic-halohydrins; oxirane ring-opening; ionic liquids; metal ion catalysis;
D O I：
10.1055/s-2006-941562
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Metal ion electrophilic catalysis (Li+ > Na+ >> K+) has been found in ring-opening reactions of 1,2-epoxides 1-5 by metal halides MHal in ionic liquids. The results have been rationalized on the basis of a transition state where the cation M+ stabilizes the negative charge developing on the oxygen atom of the oxirane ring while favoring the nucleophilic attack at the adjacent carbon by the ion-paired anion Hal(-).
引用
收藏
页码：1335 / 1338
页数：4
相关论文
共 20 条
  • [1] REGIOCHEMICAL CONTROL OF THE RING-OPENING OF 1,2-EPOXIDES BY MEANS OF CHELATING PROCESSES .10. SYNTHESIS AND RING-OPENING REACTIONS OF MONOFUNCTIONALIZED AND DIFUNCTIONALIZED CIS AND TRANS ALIPHATIC OXIRANE SYSTEMS
    AZZENA, F
    CALVANI, F
    CROTTI, P
    GARDELLI, C
    MACCHIA, F
    PINESCHI, M
    [J]. TETRAHEDRON, 1995, 51 (38) : 10601 - 10626
  • [2] A HIGHLY REGIOSELECTIVE CONVERSION OF EPOXIDES TO HALOHYDRINS BY LITHIUM HALIDES
    BAJWA, JS
    ANDERSON, RC
    [J]. TETRAHEDRON LETTERS, 1991, 32 (26) : 3021 - 3024
  • [3] Hydrophobic, highly conductive ambient-temperature molten salts
    Bonhote, P
    Dias, AP
    Papageorgiou, N
    Kalyanasundaram, K
    Gratzel, M
    [J]. INORGANIC CHEMISTRY, 1996, 35 (05) : 1168 - 1178
  • [4] AN EASY PROCEDURE FOR THE HIGHLY REGIOSELECTIVE CONVERSION OF EPOXIDES TO HALOHYDRINS
    BONINI, C
    GIULIANO, C
    RIGHI, G
    ROSSI, L
    [J]. SYNTHETIC COMMUNICATIONS, 1992, 22 (13) : 1863 - 1870
  • [5] REGIOSELECTIVE OPENING OF EPOXY ALCOHOLS - MILD CHEMOSELECTIVE AND STEREOSELECTIVE PREPARATION OF IODOHYDRINS AND 1,2-DIOLS
    BONINI, C
    RIGHI, G
    SOTGIU, G
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (21) : 6206 - 6209
  • [6] Ionic liquids: solvent properties and organic reactivity
    Chiappe, C
    Pieraccini, D
    [J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2005, 18 (04) : 275 - 297
  • [7] Macrocyclic polyethers as enolate activators in base-catalyzed phase-transfer reactions
    Gobbi, A
    Landini, D
    Maia, A
    Petricci, S
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (16) : 5356 - 5361
  • [8] A first theoretical study on the origin of the metal-mediated regioselective opening of 2,3-epoxy alcohols
    Infante, I
    Bonini, C
    Lelj, F
    Righi, G
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (10) : 3773 - 3780
  • [9] Solvent-free organic reactions on silica gel supports.: Facile transformation of epoxides to β-halohydrins with lithium halides
    Kotsuki, H
    Shimanouchi, T
    Ohshima, R
    Fujiwara, S
    [J]. TETRAHEDRON, 1998, 54 (12) : 2709 - 2722
  • [10] Anion nucleophilicity in ionic liquids: a comparison with traditional molecular solvents of different polarity
    Landini, D
    Maia, A
    [J]. TETRAHEDRON LETTERS, 2005, 46 (23) : 3961 - 3963
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