Electrochemical Difluoromethylation of Electron-Deficient Alkenes.

Electrochemical 1,2-hydroxydifluoromethylation and C-H difluoromethylation of acrylamides were developed by using CF HSO NHNHBoc as the source of the CF H group. These electricity-powered oxidative alkene functionalization reactions do not need transition-metal catalysts or chemical oxidants. The reaction outcome, 1,2-difuntionalization or C-H functionalization, is determined by the substituents on the amide nitrogen atom of the acrylamides instead of by the reaction conditions.

Electrochemical Difluoromethylarylation of Alkynes.

An unprecedented radical difluoromethylarylation reaction of alkynes has been developed by discovering a new difluoromethylation reagent, CFHSONHNHBoc. This air-stable and solid reagent can be prepared in one step from commercially available reagents CFHSOCl and NHNHBoc. The CFH radical, generated through ferrocene-mediated electrochemical oxidation, participates in an unexplored alkyne addition reaction followed by a challenging 7-membered ring-forming homolytic aromatic substitution step to afford fluorinated dibenzazepines.

Metal- and Reagent-Free Intramolecular Oxidative Amination of Tri- and Tetrasubstituted Alkenes.

A metal- and reagent-free, electrochemical intramolecular oxidative amination reaction of tri- and tetrasubstituted alkenes has been developed. The electrosynthetic method proceeds through radical cyclization to form the key C-N bond, allowing a variety of hindered tri- and tetrasubstituted olefins to participate in the amination reaction. The result is the efficient synthesis of a host of alkene-bearing cyclic carbamates and ureas and lactams.