title: Stereoselective nucleophilic fluoromethylation of aryl ketones: dynamic kinetic resolution of chiral α-fluoro carbanions.
abstract: 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.
authors.affiliation: Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032 (China) http://hujinbo.sioc.ac.cn/en/
authors.forename: Xiao
authors.initials: X
authors.lastname: Shen
authors.forename: Wenjun
authors.initials: W
authors.lastname: Miao
authors.forename: Chuanfa
authors.initials: C
authors.lastname: Ni
authors.forename: Jinbo
authors.initials: J
authors.lastname: Hu
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000838:Anions / Q000737:chemistry; D005461:Fluorine / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D008745:Methylation; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000838:Anions; D007659:Ketones; D005461:Fluorine
keywords: alcohols; chirality; fluoromethylation; stereoselective addition; sulfoximine