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Download fileEnantioselective Baeyer–Villiger Oxidation: Desymmetrization of Meso Cyclic Ketones and Kinetic Resolution of Racemic 2‑Arylcyclohexanones
journal contribution
posted on 2012-10-17, 00:00 authored by Lin Zhou, Xiaohua Liu, Jie Ji, Yuheng Zhang, Xiaolei Hu, Lili Lin, Xiaoming FengCatalytic enantioselective Baeyer–Villiger (BV)
oxidations
of racemic and meso cyclic ketones were achieved in the presence of
chiral N,N′-dioxide–ScIII complex catalysts. The BV oxidations of prochiral cyclohexanones
and cyclobutanones afforded series of optically active ε- and
γ-lactones, respectively, in up to 99% yield and 95% ee. Meanwhile,
the kinetic resolution of racemic 2-arylcyclohexanones was also realized
via an abnormal BV oxidation. Enantioenriched 3-aryloxepan-2-ones,
whose formation is counter to the migratory aptitude, were obtained
preferentially. Both the lactones and the unreacted ketones were obtained
with high ee values.