Amino acid-functionalized cyclopentadienyl molybdenum tricarbonyl complex and its use in catalytic olefin epoxidation

The complex [(N-benzyloxycarbonylprolyl)cyclopentadienyl]-Mo(CO)3Me was prepared by the reaction of the amino acid-functionalized cyclopentadienyl-lithium reagent with Mo(CO)6, and subsequent methylation with CH3I. The complex was characterized by FTIR, 1H and 13C NMR, and elemental analysis. A single-crystal X-ray diffraction study showed that the complex is chiral, crystallizing in the orthorhombic P212121 space group with the Flack parameter refining to –0.007(16), which unequivocally confirms the presence of an enantiomerically pure compound. The complex was examined as a catalyst precursor in the liquid-phase epoxidation of trans-β-methylstyrene at 280–330 K, using either tert-butylhydroperoxide (tert-BuOOH), cumylhydroperoxide or urea-hydrogen peroxide adduct as oxidant, and, optionally, a co-solvent. With chloroform and tert-BuOOH, the catalytic activity surpasses that previously reported for chiral complexes of the type CpMo(CO)3X, giving the epoxide isomers ((R,R)-(+) and (S,S)-(−)-1-phenylpropylene oxide) in excellent selectivity, albeit with negligible enantiomeric excess. FTIR spectroscopy showed that the oxidative decarbonylation of the tricarbonyl complex with tert-BuOOH is fast under the reaction conditions used, and that the structural integrity of the amino acid-functionalized cyclopentadienyl group is retained during this process. The use of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate as a solvent for the catalyst generates a biphasic liquid–liquid reaction system that enables, at the end of a catalytic cycle, the separation and reutilization of the catalyst.

Graphical abstractAn amino acid-functionalized cyclopentadienyl molybdenum tricarbonyl complex, [(N-benzyloxycarbonylprolyl)-cyclopentadienyl]Mo(CO)3Me, was successfully synthesized and applied as a catalyst precursor in the epoxidation of trans-β-methylstyrene under mild conditions, using tert-butylhydroperoxide as oxidant.Figure optionsDownload full-size imageDownload as PowerPoint slide