Formic Acid: A Promising Bio‐Renewable Feedstock for Fine Chemicals

Abstract

In light of the growing scarcity of petroleum-based raw materials, carbon dioxide (CO2) is becoming increasing attractive as organic carbon source. In this perspective, formic acid (HCOOH) might be an interesting bio-renewable solution to store, transport, and activate carbon dioxide for the synthesis of value-added chemicals. Herein, HCOOH has been successfully used as C1 building block for the synthesis of a library of alcohols via a catalysed oxo-synthesis, under green experimental conditions

Effect of Annealing Treatment on Electrocatalytic Properties of Copper Electrodes toward Enhanced CO2 Reduction

“…Formic acid is one of the most valuable CO 2 RR products, since it can be used as a building block for fine chemicals . Moreover, formic acid can be used in low‐temperature direct fuel cells, with higher efficiency than other C1 and C2 liquid alcohol fuels .…”

“…Formic acid is one of the most valuable CO 2 RR products, since it can be used as a building block for fine chemicals. [29] Moreover, formic acid can be used in low-temperature direct fuel cells, with higher efficiency than other C1 and C2 liquid alcohol fuels. [30][31][32][33] In this context, it is still necessary to develop catalysts with onset potential and current densities optimized for CO 2 RR.…”

Regioselective Pd‐Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

“…[6] Additionally, olefin carbonylation reactions in the presence of formic acid as a carbonyl source are also achieved through sequential dehydrogenation and reverse water gas shift processes at elevated temperature (> 150 8C). [7] Moreover, formates (F; R = alkyl, aryl) [8] and formamides (G) [9] have also been used for the carbonylation of olefins and aryl halides. In general, harsh conditions, poor selectivity in the presence of additional nucleophiles, and/or the necessity for external CO pressure restrict the further application of formic acid derivatives as a CO source.…”

“…[6] Additionally,o lefin carbonylation reactions in the presence of formic acid as acarbonyl source are also achieved through sequential dehydrogenation and reverse water gas shift processes at elevated temperature (> 150 8 8C). [7] Moreover, formates (F;R=alkyl, aryl) [8] and formamides (G) [9] have also been used for the carbonylation of olefins and aryl halides.I ng eneral, harsh conditions,p oor selectivity in the presence of additional nucleophiles,a nd/or the necessity for external CO pressure restrict the further application of formic acid derivatives as aC Os ource.C O 2 ( H )i sa ni deal C1 building block in organic synthesis due to its abundance, nontoxicity,a nd recyclability.R emarkably,t he catalytic in situ generation of CO from CO 2 reduction and its incorporation in the following carbonylation reactions has been realized. [10] This is ap romising process that uses CO 2 instead of CO as aC 1 resource for carbonylations,b ut the substrate scope is so far limited by the required reductants and the regioselectivity cannot so far be controlled.…”

A recyclable CO surrogate in regioselective alkoxycarbonylation of alkenes: indirect use of carbon dioxide

“…4 Thus, a number of CO surrogates have been applied in the carbonylation reactions of alkenes over the years. Most recent developments include the use of formates, 5 formic acid, 6 formaldehyde, 7 alcohols 8 and the greenhouse gas carbon dioxide. 9 However, most transformations are performed under forcing conditions (temperatures >100 °C, high catalyst loading) and even if cheap, low--weight carbonylation reagents are used, the overall atom economy is deteriorated due to the employment of overstoichiometrical amounts of the CO surrogate.…”