Catalytic Fluorination of α-Branched Ketones with Nucleophilic Fluorine.

We herein disclose the first example of metal-free, redox-umpolung-enabled catalytic fluorination of α-branched ketones with nucleophilic fluorine by the judicious choice of an oxidant. The strategic use of cyclopropyl malonoyl peroxide in hypervalent iodine(III) catalysis expands the modularity and generality in the construction of α-fluorinated ketones with ideally orthogonal reactivity space, avoiding competing oxidation processes. Characteristic for this transformation is its operational simplicity, mild reaction conditions, and gram-scale synthetic ability.