Ring opening reactions of 1,2-epoxides catalyzed by complexes of polyether ligands with metal halides in low polarity solvents. Comparison with heterogeneous systems

被引:7
作者
Landini, D
Maia, A [1 ]
Pinna, C
机构
[1] CNR, Ist Sci & Tecnol Mol, Via Golgi 19, I-20133 Milan, Italy
[2] Univ Milan, Dipartimento Chim Organ & Ind, I-20133 Milan, Italy
关键词
epoxides; oxirane ring opening; metal ion catalysis; solid-liquid phase transfer catalysis; polyether ligands;
D O I
10.3998/ark.5550190.0005.317
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Metal ion electrophilic catalysis has been revealed in ring opening reactions of 1,2-epoxides 1-5 promoted by complexes of polyethers 6-9 with alkali metal halides MHal (M+ = Li+, Na+, K+; Hal(-) = I-, Br-) in solvents of low polarity (chlorobenzene, 1,2-dichlorobenzene). The catalytic effect depends on the Lewis acid character of the cation (K+ <<Na+ < Li+) as well as on the ligand topology (open-chain > cyclic polyether). Results have been rationalized on the basis of a transition state where the complexed cation (M+ subset of Lig) stabilizes the negative charge developing on the oxygen atom of the oxirane ring while favors the nucleophilic attack at the adjacent carbon by the halide anion Hal(-).
引用
收藏
页码:202 / 212
页数:11
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