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Stereoselective Nucleophilic Fluoromethylation of Aryl Ketones: Dynamic Kinetic Resolution of Chiral α-Fluoro Carbanions


  • Support of our work by the National Basic Research Program of China (2012CB215500 and 2012CB821600), the National Natural Science Foundation of China (20825209 and 21372246), the Chinese Academy of Sciences, and the Syngenta PhD Studentship (to X.S.) is gratefully acknowledged.


Although many methods are available for the synthesis of optically enriched monofluoromethyl secondary alcohols, synthesizing optically enriched monofluoromethyl tertiary alcohols remains a challenge. An efficient and easy-to-handle nucleophilic fluoromethylation protocol was developed. The current monofluoromethylation showed much higher facial selectivity than the corresponding difluoromethylation and proceeded via a different type of transition state. Excellent stereoselective control at the fluorinated carbon chiral center was found, an effect believed to be facilitated by the dynamic kinetic resolution of the chiral α-fluoro carbanions.