88817-90-7Relevant academic research and scientific papers
Effect of the leaving group on the rate and mechanism of the palladium-catalyzed isomerization of cyclic allylic benzoates in allylic substitutions
Amatore, Christian,Jutand, Anny,Mensah, Laure,Meyer, Gilbert,Fiaud, Jean-Claude,Legros, Jean-Yves
, p. 1185 - 1192 (2007/10/03)
In chloroform, the reaction of cis-5-phenylcyclohex-2-enyl 4-Z-benzoate (cis-1z, Z = NO2, Cl, H, Me, MeO) with Pd0 complexes ligated to PPh3 is reversible and proceeds with isomerization at the allylic position.
Regio- and sterochemistry of alkylation of benzoate anion with 5-phenyl 2-cyclohexenyl sulfonium salts : influence of copper(I)
Gauchet, Frederic,Julia, Marc,Mestdagh, Helene,Rolando, Christian
, p. 1036 - 1044 (2007/10/02)
In order to invstigate the regio and stereochemistry of uncatalyzed and copper(I) catalyzed substitution reactions on allylic sulfonium salts, cis and trans 5-phenyl 2-cyclohexenyldimethylsulfonium tetrafluoroborates were synthesized, along with their α and γ-deutterated analogs.Uncatalyzed substitution of benzoate anion on these substrates essentially involves anti α attack (SN2 reaction), with a minor amount of syn γ (SN2') reaction in the case of the trans substrate.On the contrary, for both stereoisomers copper(I) catalyzed benzoate substitution displays anti attack with (50:50) α,γ-regiochemistry.The mechanism of this copper(I) catalyzed reaction is discussed: it necessarily involves a symmetrical intermediate, possibly a ?-allyl copper complex.
