N-bonded enolatorhenium(I) complexes having dimethylphenylphosphine ligands as active key intermediates in catalytic Knoevenagel and Michael reactions

被引：21

作者：

Hirano, M ^{[1
]}

Hirai, M ^{[1
]}

Ito, Y ^{[1
]}

Tsurumaki, T ^{[1
]}

Baba, A ^{[1
]}

Fukuoka, A ^{[1
]}

Komiya, S ^{[1
]}

机构：

[1] Tokyo Univ Agr & Technol, Fac Technol, Dept Appl Chem, Koganei, Tokyo 1848588, Japan

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1998年 / 569卷 / 1-2期

关键词：

rhenium dinitrogen complex; rhenium enolate complex; crystal structure; Knoevenagel reaction; Michael reaction;

D O I：

10.1016/S0022-328X(98)00768-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Enolatorhenium(I) complexes cis-Re(NCCRCO2R')(NCCHRCO2R')(PMe2Ph)(4) (R = H, R' = Me (2a); R = H, R' = Et (2b); R = H, R' = n-Bu (2c); R = Me, R' = Et (2d)) are prepared by the reaction of ReH(N-2)(PMe2Ph)(4) (1) with alkyl cyanoalkyl carboxylate. X-ray structure analysis of 2b shows that it has an octahedral Re geometry, where mutually cis enolato and ester ligands bind to the rhenium via cyano groups. Reaction of 2b with benzaldehyde gives Re(NCCHCO3Et)[NC(EtO2C)C-CHPh]-(PMe2Ph)(4) (4), which is also derived from the ligand exchange reaction of 2b with ethyl (E)-2-cyano-3-phenylpropenoate. These rhenium(I) complexes 1, 2, and 4 catalyze Knoevenagel and Michael reactions under neutral and mild conditions. A possible mechanism for the Knoevenagel reaction has been proposed. (C) 1998 Elsevier Science S.A. All rights reserved.

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页码：3 / 14

页数：12

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