153814-39-2Relevant articles and documents
Novel Catalytic Metathesis of Substituted Olefins Promoted by Rhenium(I) Enolate Complexes
Hirano, Masafumi,Hirai, Miwa,Ito, Yuji,Fukuoka, Atsushi,Komiya, Sanshiro
, p. 165 - 166 (1994)
Rhenium(I) enolate complexes Re(NCCHCO2Et)(PMe2Ph)4 and Re(NCCHCO2Et)(NCCH2CO2Et)(PMe2Ph)4 are found to catalyze unique olefin metathesis reaction of tetracyanoethylene with ethyl α-cyanocinnamate to give 1,1-dicyano-2-phenylethylene and ethyl 2,3,3-tricyanopropenoate at room temperature.
N-bonded enolatorhenium(I) complexes having dimethylphenylphosphine ligands as active key intermediates in catalytic Knoevenagel and Michael reactions
Hirano, Masafumi,Hirai, Miwa,Ito, Yuji,Tsurumaki, Tsutomu,Baba, Atsushi,Fukuoka, Atsushi,Komiya, Sanshiro
, p. 3 - 14 (2007/10/03)
Enolatorhenium(I) complexes cis-Re(NCCRCO2R′)(NCCHRCO2R′)(PMe 2Ph)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(N2)(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(NCCHCO2Et)[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.
