Radical Cross-Coupling Reaction Based on Hydrogen Atom Abstraction of DMF and Decarboxylation of α-Ketoacid under Electricity

Abstract

The cleavage of DMF into a dimethyl carbamoyl radical under mild electrochemical conditions was revealed for the first time. Meanwhile, an electrochemical decarboxylation of αketoacid occurred to produce an acyl radical. The radical crosscoupling reaction of these two electron-deficient acyl radicals was carried out with high selectivity. This discovery provides a new electrochemical way for the cracking of DMF, and a milder and safer method for its application in organic synthesis.

Fully biomass-based biodegradable polymers from lignin and raw castor oil: lignin-graft-castor oil

“…In some cases, the cleavage of dimethylformamide (DMF) into a dimethyl carbamoyl radical can occur during certain reactions. 36 The coupling reaction of DMF weakens the sustainable chemistry aspect. To address this concern, the solvent DMF can be replaced by two biobased aprotic dipolar solvents, Cyrene™ and γ-valerolactone (GVL), which have previously been reported as alternatives to DMF.…”

Electrochemical Formation of α-Ketoamides from Ketoximes through Non-Beckmann Mechanism Pathway

“…13 C{ 1 H} NMR (125 MHz, CDCl 3 ) δ 190.1, 166.8 (d, J = 257.7 Hz), 166.8, 132.7 (d, J = 9.7 Hz), 129.8, 116.5 (d, J = 22.1 Hz), 37.2, 34.2 Known compound. 51 2-(4-Chlorophenyl)-N,N-dimethyl-2-oxoacetamide (3f). Yellow oil (158 mg, 75%).…”

“…1 H NMR (500 MHz, CDCl 3 ) δ 7.94 (d, J = 7.9 Hz, 2H), 7.64 (t, J = 7.5 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 3.12 (s, 3H), 2.96 (s, 3H). 13 51 2-(4-Methoxyphenyl)-N,N-dimethyl-2-oxoacetamide (3c). Yellow oil (184 mg, 89%).…”

Visible‐Light‐Mediated Synthesis of α‐Ketoamides via Oxidative Amination of 2‐Bromoacetophenones Using Eosin Y as a Photoredox Catalyst

“…[8] Wang and Gong have illustrated an electrochemical cross-coupling of a carbamoyl radical with an acyl radical to form α-ketoamides involving hydrogen atom abstraction of DMF and decarboxylation of α-ketoacid. [9] Hashmi and co-workers have reported a two-step gold-catalyzed protocol involving the reaction of a bromoalkyne with anthranils. [10] Recently, Liu and Zhou have reported a copper-catalyzed amidation of sulfoxonium ylides to access α-ketoamides in one step via CÀ H and CÀ N bond activation by O 2 as oxidant.…”

“…have explored a selective amidation of 1,3‐dicarbonyl compounds via photocatalyzed umpolung reaction to synthesize α‐ketoamides [8] . Wang and Gong have illustrated an electrochemical cross‐coupling of a carbamoyl radical with an acyl radical to form α‐ketoamides involving hydrogen atom abstraction of DMF and decarboxylation of α‐ketoacid [9] . Hashmi and co‐workers have reported a two‐step gold‐catalyzed protocol involving the reaction of a bromoalkyne with anthranils [10] .…”