Homogeneous Catalysis for the Conversion of CO₂, CO, CH₃OH, and CH₄ to C₂₊ Chemicals via C–C Bond Formation

Abstract

In the past few decades, the advances of CO 2 reduction have been mostly focused on the synthesis of C 1 products, such as CO, formic acid, methanol, and methane. However, the syntheses of C 2+ products from generally abundant C 1 sources such as CO 2 , CO, and CH 4 are traditionally more difficult because they involve two selective processes: activation of the C 1 source and simultaneous C−C bond formation. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of C 1 sources to higher-energy C 2+ products under mild conditions. Moreover, the recent expansion of these mechanistically different methods has enabled the use of various C 1 sources to undergo either homocoupling or heterocoupling via C−C bond formation to generate various C 2+ products. In this review, we systematically present the various advances in C 1 to C 2+ conversions under homogeneous catalysis.

Materials Design for Photocatalytic CO2 Conversion to C2+ Products

“…Typically, the stabilization of these intermediates facilitates C−C coupling on the photocatalyst surface, ultimately resulting in the production of valuable C 2+ products (Figure 3 and Table 2). 24,25 In greater detail, the currently reported processes for C−C coupling encompass (a) the dimerization of *CO (*CO−*CO coupling), (b) the hydrogenation of *CO to *CHO (hydroxymethylidyne) and the subsequent *CO−*CHO coupling (forming *COCHO), 26 (c) the dimerization of *CHO (*CHO−*CHO coupling), 27 and (d) the *CH 3 −*CH 3 coupling (for C 2 H 6 production). The C−C coupling products (i.e., C 2+ intermediates including hydrocarbons and oxygenates) formed in these processes undergo a further proton-coupled electron transfer process to be transformed into various end products.…”

Establishing the main determinants of the environmental safety of catalytic fine chemical synthesis with catalytic cross-coupling reactions

“…The advancement of modern organic synthesis is intrinsically connected to the development of efficient methodologies for carbon-carbon bond formation, allowing the construction of intricate molecular architectures. [1][2][3][4][5][6][7] However, despite their enormous popularity both in laboratory practice and industry, these methodologies also demand a conscientious evaluation of their safety and environmental impact. [8][9][10][11] Among the recognized transformative cross-coupling reactions, the Sonogashira and Mizoroki-Heck reactions stand out for their ability to forge carbon-carbon bonds under mild conditions.…”

Paired Electrosynthesis of Formaldehyde Derivatives from CO2 Reduction and Methanol Oxidation

“…[8,[17][18][19][20] On the other hand, the direct reduction of CO 2 to aldehydes to be utilized as both a fuel and a chemical building block is a process adopted by nature. [21,22] Plants utilize a strategy of activation, followed by a subsequent reduction for the synthesis of sugars, which are aldehydes, as energy sources and structural building blocks. In detail, the Calvin cycle is a series of biochemical reactions, [23][24][25] in which the carboxylic acid phosphoglyceric acid (PGA) that results from the insertion of CO 2 into ribulose 1,5-biphosphate (RuBP) is activated to the phosphate ester bisphosphoglycerate (BPG) before being reduced to an aldehyde, glyceraldehyde-3phosphate (G3P).…”