Efficient Electrocatalysis for the Preparation of (Hetero)aryl Chlorides and Vinyl Chloride with 1,2-Dichloroethane.

Although the application of 1,2-dichloroethane (DCE) as a chlorinating reagent in organic synthesis with the concomitant release of vinyl chloride as a useful byproduct is a fantastic idea, it still presents a tremendous challenge and has not yet been achieved because of the harsh dehydrochlorination conditions and the sluggish C-H chlorination process. Here we report a bifunctional electrocatalysis strategy for the catalytic dehydrochlorination of DCE at the cathode simultaneously with anodic oxidative aromatic chlorination using the released HCl as the chloride source for the efficient synthesis of value-added (hetero)aryl chlorides. The mildness and practicality of the protocol was further demonstrated by the efficient late-stage chlorination of bioactive molecules.

Selective α-Oxyamination and Hydroxylation of Aliphatic Amides.

Compared to the α-functionalization of aldehydes, ketones, even esters, the direct α-modification of amides is still a challenge because of the low acidity of α-CH groups. The α-functionalization of N-H (primary and secondary) amides, containing both an unactived α-C-H bond and a competitively active N-H bond, remains elusive. Shown herein is the general and efficient oxidative α-oxyamination and hydroxylation of aliphatic amides including secondary N-H amides. This transition-metal-free chemistry with high chemoselectivity provides an efficient approach to α-hydroxy amides. This oxidative protocol significantly enables the selective functionalization of inert α-C-H bonds with the complete preservation of active N-H bond.

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-RF and C-N3 bonds from the C═C moiety. A variety of fluoroalkyl groups including the CF3 group can be selectively introduced to olefins to afford a series of ß-fluoroalkylated azides.