Silver encapsulated copper salen complex: efficient catalyst for electrocarboxylation of cinnamyl chloride with CO₂

Abstract

An active catalyst, [Cu]@Ag composite, was synthesized for the first time and used as a cathode for electrocarboxylation of cinnamyl chloride with CO 2 . b,g-Unsaturated carboxylic acids were obtained with excellent yield and moderate selectivity. Moreover, reasonable yields and selectivities of carboxylic acids were also achieved with several allylic halides and aryl halides.Scheme 1 Regiodivergency in allyl electrophiles and our concept of the allylation of CO 2 .

Electrochemical Approaches to Carbonylative Coupling Reactions

“…In 2019, the Lu group prepared a silver‐coated copper salen catalyst for the first time using a doping method for the electrocarboxylation of cinnamoyl chloride and carbon dioxide. This catalyst had applicability to a variety of substrates, and the yield was close to 70% (Scheme 19 Lu) [87] . In the same year, Mellah and his colleagues developed a halide carboxylation system using samarium as a sacrificial anode.…”

“…This catalyst had applicability to a variety of substrates, and the yield was close to 70% (Scheme 19 Lu). [87] In the same year, Mellah and his colleagues developed a halide carboxylation system using samarium as a sacrificial anode. Unlike sacrificial anodes such as magnesium and aluminum, the oxidation product of Sm(II) could activate carbon dioxide to drive the entire reaction.…”

Recent Advances in the Catalytic Umpolung Carboxylation of Allylic Alcohol Derivatives with Carbon Dioxide

“…In 2019, Wang, Lu, and co‐workers discovered that a silver encapsulated Cu(II)‐salen complex ([Cu]@Ag) is a suitable cathode for the electrochemical allylic carboxylation of allyl chlorides, bromides, and iodides with CO 2 (Figure 19). [37] The Cu(II)‐salen complex is reduced to Cu(I)‐salen, which undergoes oxidative addition with allyl chloride to afford an allyl Cu(III) species. Further reduction of the allyl Cu(III) species by electrons affords an allyl anion species.…”

Homogeneous and heterogeneous molecular catalysts for electrochemical reduction of carbon dioxide

“…Other promising active electrocatalytic systems incorporate Ag metal centers or Ag electrodes. 47,63,[144][145][146][147] Compared to Au electrocatalysts, Ag catalyst are cheaper and have comparable activity.…”