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A novel protocol for the transition metal‐free 1,2‐addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho‐F substituents on the polyfluorophenyl boronates and the counterion K+ in the carbonate base are critical. The distinguishing features...