Synthesis of 3-Formylindoles via Electrochemical Decarboxylation of Glyoxylic Acid with an Amine as a Dual Function Organocatalyst.

A new method for 3-formalytion of indoles has been developed through electrochemical decarboxylation of glyoxylic acid with the amine as a dual function organocatalyst. The amine facilitated both the electrochemical decarboxylation and the nucleophilic reaction efficiently, whose loading can be as low as 1 mol %. This protocol has a broad range of functional group tolerance under ambient conditions. The gram-scale experiment has shown great potential in the synthetic application of this strategy.

Electrosynthesis of ( E)-Vinyl Thiocyanates from Cinnamic Acids via Decarboxylative Coupling Reaction.

Thiocyanate compounds are key intermediates in the synthesis of pharmaceuticals and other sulfur-containing organic compounds. Herein, we first report an electrochemical protocol to synthesize vinyl thiocyanates from decarboxylative coupling of cinnamic acids with NH4SCN in aqueous solution. This method provides thiocyanation products with broad functional group tolerance under ambient conditions.

Electrochemical N-Formylation of Amines via Decarboxylation of Glyoxylic Acid.

A new method for the synthesis of formamides has been developed through electrochemical decarboxylative N-formylation of amines with glyoxylic acid. This protocol provides an efficient approach to formamides with a broad range of functional group tolerance under ambient conditions.

Electrochemical Decarboxylative Sulfonylation of Cinnamic Acids with Aromatic Sulfonylhydrazides to Vinyl Sulfones.

A stereoselective synthesis of (E)-vinyl sulfones has been developed via electrochemical oxidative N-S bond cleavage of aromatic sulfonylhydrazides, followed by cross-coupling reactions with cinnamic acids to form the C-S bond. The protocol proceeded smoothly to afford (E)-vinyl sulfones in good yields with wide substrate scope under metal-free and halogen-free conditions.

Copper-Catalyzed Decarboxylative Difluoroalkylation and Perfluoroalkylation of α,ß-Unsaturated Carboxylic Acids.

Copper-catalyzed decarboxylative difluoroalkylation and perfluoroalkylation of α,ß-unsaturated carboxylic acids is described. Promoted by dialkyl phosphite, this novel reaction affords fluoroalkylated motifs with excellent stereoselectivity and broad substrate scope under mild reaction conditions from readily available fluoroalkyl iodides and bromides. Preliminary mechanism study suggests that radical pathway was involved in the catalytic cycle and dialkyl phosphite had played an indispensable role in this reaction.