Reductive functionalization of CO₂ with amines: an entry to formamide, formamidine and methylamine derivatives

Abstract

International audienceCO2 utilization for the production of C1-containing molecules is a desirable route to value-added chemicals. In this perspective, we summarize the recent results devoted to the formation of nitrogen compounds obtained by reductive functionalization of CO2 in the presence of amines. Using mild reductants, such as molecular hydrogen, hydrosilanes and hydroboranes, novel catalytic reactions have been designed in the last few years to facilitate the reductive functionalization of CO2 to formamide, formamidine and methylamine derivatives. While early efforts were devoted to the formylation of N-H bonds, efficient organic and metal catalysts have been developed lately to promote the complete deoxygenation of CO2 to benzimidazoles, quinazolinones, formamidines and methylamines. Finally, the opportunities and challenges facing the practical use of CO2 in the production of nitrogen-containing molecules are discussed

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

“…(4), 26) and related derivatives to form carbamates (27). The chemical reduction of carbamate-related species has been recently reviewed elsewhere [49]. Highly nucleophillic primary amines have been shown to react with CO 2 to form urea derivatives in a formal 2e À reduction process [50].…”

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

“…From this perspective, there have been various attempts at N-methylation by using a C 1 -building block source (CO 2 , formic acid) and/or a reductant (H 2 , silanes and boranes) with organometallic catalysts, including rhodium, ruthenium and zinc complexes. 1,3,[9][10][11][12][13][14] However, these homogenous catalysts require challenging synthesis processes with an elaborately designed ligand complex, which is difficult to separate and recycle from the products. 15 Furthermore, additives such as organic acids are needed for good performance, and high pressure and/or temperature are required.…”

Reaction Mechanisms of CO2 Reduction to Formaldehyde Catalyzed by Hourglass Ru, Fe, and Os Complexes: A Density Functional Theory Study

“…As an abundant and non-toxic C 1 -building block, carbon dioxide can be reduced to various chemicals, such as carbon monoxide [1], methanol [2], formaldehyde [3], acetals [4,5], formic acid [5], formate [6,7], formamides [8], methylamines [8], formamidines [8], imines [3] and methane [9]. Recently, Beller and co-workers [10] reported the methylation of aromatic C-H bonds using CO 2 and H 2 with the assistance of a ruthenium triphos catalyst.…”