title: Enantioselective Baeyer-Villiger oxidation: desymmetrization of meso cyclic ketones and kinetic resolution of racemic 2-arylcyclohexanones.
abstract: Catalytic enantioselective Baeyer-Villiger (BV) oxidations of racemic and meso cyclic ketones were achieved in the presence of chiral N,N'-dioxide-Sc(III) 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.
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China.
authors.forename: Lin
authors.initials: L
authors.lastname: Zhou
authors.forename: Xiaohua
authors.initials: X
authors.lastname: Liu
authors.forename: Jie
authors.initials: J
authors.lastname: Ji
authors.forename: Yuheng
authors.initials: Y
authors.lastname: Zhang
authors.forename: Xiaolei
authors.initials: X
authors.lastname: Hu
authors.forename: Lili
authors.initials: L
authors.lastname: Lin
authors.forename: Xiaoming
authors.initials: X
authors.lastname: Feng
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D003512:Cyclohexanones / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D003512:Cyclohexanones; D009942:Organometallic Compounds