Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the α-Fluorination of Ketenes: Synthetic and Mechanistic Studies

Sarah Yunmi Lee, Stefan Neufeind and Gregory C. Fu*

*Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States, Email: gcfucaltech.edu

S. Y. Lee, S. Neufeind, G. C. Fu, J. Am. Chem. Soc., 2014, 136, 8899-8902.

DOI: 10.1021/ja5044209

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Abstract

A catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C₆F₅ONa furnishes tertiary α-fluoroesters. Mechanistic studies suggest that the addition of an external nucleophile (C₆F₅ONa) is critical for turnover, releasing the catalyst from an N-acylated intermediate.

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Key Words

α-fluoroesters, N-fluorobenzenesulfonimide

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ID: J48-Y2014