Unusual Behavior of a Novel Heterogeneous Chiral Dimer Cr(III)−Salen Complex in the Epoxidation/Epoxide Ring-Opening Reaction of trans -Methylcinnamate Ester

A dimer chromium(III)−salen complex immobilized on modified silica is an effective catalyst for the epoxidation/epoxide ring-opening reaction of trans -methylcinnamate ester and gave significantly high ee in methyl (2 R,3 S )-2,3-dihydroxy-3-phenylpropionate. For the first time, it is shown that a donor ligand (e.g., Et 3 N) can be involved into the enantioselective mechanism of the product configuration. It is suggested that the additive is interacting with the reaction intermediate in a manner that prolongs its lifetime, thus affording a free rotation of the C−C single bond in this species and a selective collapse to the cis -epoxide product. In the presence of water, this epoxide led to methyl (2 S,3 R )-2,3-dihydroxy-3-phenylpropionate. Alternatively, the donor additives may give rise to a new chromium-based oxidant that effects epoxidation and its consecutive ring opening to diols via an unusual pathway.