Transition‐Metal‐Free Acceptorless Decarbonylation of Formic Acid Enabled by a Liquid Chemical‐Looping Strategy

Abstract

The selective decarbonylation of formic acid was achieved under transition‐metal‐free conditions. Using a liquid chemical‐looping strategy, the thermodynamically favored dehydrogenation of formic acid was shut down, yielding a pure stream of CO with no H2 or CO2 contamination. The transformation involves a two‐step sequence where methanol is used as a recyclable looping agent to yield methylformate, which is subsequently decomposed to carbon monoxide using alkoxides as catalysts.

Catalytic carbonylation of acrylic acid to succinic anhydride

“…The decarbonylation of formic acid, a C1 chemical which can derive from biomass or CO2 electroreduction, [23] was performed, using methyl formate as a recyclable intermediate (Figure 2, top). [24] The reaction was setup using the standard conditions, then the atmosphere of the autoclave was purged with H2, and finally 16 bar of CO, previously synthesized via the methoxide-catalyzed decarbonylation of methyl formate, were introduced. After 6 h at 90 °C, SA was formed in 77 % yield, together with 4 % of monomethyl hydrogen succinate.…”

A New Route toE‐Stilbenes through the Transition‐Metal‐Free KOtBu/DMF‐Promoted Direct Coupling of Alcohols with Phenyl Acetonitriles

“…Yield of 3 aa [%] [b] 1 KO (Scheme 2). [20] 6 ay, In the presence of base would then lead to the olefination product 3 ay. The alkyl formate 5 y would be obtained from the reaction of the alcoholate 2'y with dimethylformamide, with the phenyl acetonitrile 1'a being deprotonated by the in situ generated potassium dimethyl amide or by KO t Bu.…”

“…In a proposed mechanism for the olefination, the deprotonated aryl acetonitrile ( 1’a ) could react with the alkyl formate 5 y to give the α‐alkylated nitrile 6 ay and potassium formate, the latter probably evolving to water and carbon monoxide (Scheme 2). [20] 6 ay , In the presence of base would then lead to the olefination product 3 ay . The alkyl formate 5 y would be obtained from the reaction of the alcoholate 2’y with dimethylformamide, with the phenyl acetonitrile 1’a being deprotonated by the in situ generated potassium dimethyl amide or by KO t Bu.…”

Synthesis of Deuterated Enaminones with High Isotopic Fidelity

“…16 The reaction of KOt-Bu with HCO 2 Me has been studied and proceeds according to the equation below. 17 Potassium methoxide is poorly soluble in THF, resulting in the formation of a white precipitate.…”

“…The gas was identified as CO by its reaction with phospho­molybdic acid–​palladium chloride reagent . The reaction of KO t- Bu with HCO 2 Me has been studied and proceeds according to the equation below . Potassium methoxide is poorly soluble in THF, resulting in the formation of a white precipitate. KO t ‐Bu + HCO 2 Me → KOMe + t ‐BuOH + CO …”