Late-Stage Halogenation of Complex Substrates with Readily Available Halogenating Reagents.

ConspectusLate-stage halogenation, targeting specific positions in complex substrates, has gained significant attention due to its potential for diversifying and functionalizing complex molecules such as natural products and pharmaceutical intermediates. Utilizing readily available halogenating reagents, such as hydrogen halides (HX), N-halosuccinimides (NXS), and dichloroethane (DCE) reagents for late-stage halogenation shows great promise for expanding the toolbox of synthetic chemists. However, the reactivity of haleniums (X, X = Cl, Br, I) can be significantly hindered by the presence of various functional groups such as hydroxyl, amine, amide, or carboxylic acid groups.

Azidofluoroalkylation of Alkenes with Simple Fluoroalkyl Iodides Enabled by Photoredox Catalysis.

A mild and efficient protocol for photoredox-catalyzed azidofluoroalkylation of simple alkenes is described with readily available fluoroalkyl iodides. This method allows for a direct and regioselective formation of C-R and C-N bonds from the C═C moiety. A variety of fluoroalkyl groups including the CF group can be selectively introduced to olefins to afford a series of β-fluoroalkylated azides.