Enantioselective Baeyer鈥揤illiger Oxidation: Desymmetrization of Meso Cyclic Ketones and Kinetic Resolution of Racemic 2-Arylcyclohexanones

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• 作者：Lin Zhou ; Xiaohua Liu ; Jie Ji ; Yuheng Zhang ; Xiaolei Hu ; Lili Lin ; Xiaoming Feng
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：October 17, 2012
• 年：2012
• 卷：134
• 期：41
• 页码：17023-17026
• 全文大小：309K
• 年卷期：v.134,no.41(October 17, 2012)
• ISSN：1520-5126

文摘

Catalytic enantioselective Baeyer鈥揤illiger (BV) oxidations of racemic and meso cyclic ketones were achieved in the presence of chiral N,N鈥?dioxide鈥揝c^III complex catalysts. The BV oxidations of prochiral cyclohexanones and cyclobutanones afforded series of optically active 蔚- and 纬-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.