Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate

Abstract

Ethyl bromodifluoroacetate (BrCFCOOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.

Base‐Promoted Formylation and N‐Difluoromethylation of Azaindoles with Ethyl Bromodifluoroacetate as a Carbon Source

“…Concerning the reaction pathway, it is not clear yet. However, based on the above experimental results and literatures, [ 24‐31 ] difluoromethylene carbene was involved as the key intermediate.…”

“…There is no substitution position on the right side, so it can only happen in the 5th position. E undergoes a dehydrofluorination reaction in a strongly alkaline medium to form ketoester F , [ 30 ] intermediate F is hydrolyzed again to obtain keto acid G , and finally, G is decarbonated again to form final product 4a . To date, this reaction has realized the conversion of aldehyde groups.…”

“…(Scheme 1). Whether it can be converted into an aldehyde group by a simple method, [ 30 ] especially when introduced into a heterocyclic compound, is a very interesting topic. Based on our previous researches on C1 chemistry, herein, we report an aldehyde production reaction using ethyl bromodifluoroacetate as a carbon source.…”

Iodine-imine Synergistic Promoted Povarov-Type Multicomponent Reaction for the Synthesis of 2,2′-Biquinolines and Their Application to a Copper/Ligand Catalytic System

“…Finally, we tried the aza-bidentate ligand-independent protocol to make arylamines N -formylation. Zhang’s work showed N ∧ N-bidentate ligands and organophosphorus ligands were effective for the N -formylation . We investigated the effect of our synthetic compounds as ligands in this reaction.…”

Efficient N-formylation of primary aromatic amines using novel solid acid magnetic nanocatalyst

“…Formamides are an important class of organic compounds which possess a very wide range of applications in synthetic chemistry such as Vilsmeier formylation reactions 1,2 and as polar solvents in various organic reactions and medicinal chemistry. 3 By statistical gures, it is found that nearly onefourth of all pharmaceuticals drugs such as paracetamol, formoterol, captopril and chloramphenicol have amide bonds (Fig.…”