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The highly C-selective difluoromethylation of β-ketoesters was achieved by combining TMSCF2Br/LiOH/N,N,N-trimethylhexadecan-1-ammonium bromide. Compared to other alkali metal salts or organic bases, lithium hydroxide, which served as a difluorocarbene activator from TMSCF2Br, was crucial in the control of high C/O regioselectivity.

Graphical abstract: Highly C-selective difluoromethylation of β-ketoesters by using TMSCF2Br/lithium hydroxide/N,N,N-trimethylhexadecan-1-ammonium bromide

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