Recent Advances in Homogeneous Carbonylation Using CO₂ as CO Surrogate

Abstract

Carbon dioxide is a sufficient and important carbon resource, which has been widely used as a C1 building block in synthetic chemistry. Carbonylations with CO are important processes in industry. However, due to the toxicity of CO, its storage and transport are problematic. Attentions are gradually focused on using other safe reagents to be the CO surrogates in carbonylation reactions. This review focuses on the summary of recent developments in using CO2 as a CO surrogate in homogeneous catalysis. Reductive processes by using H2, Si‐H, alcohols, etc and redox‐neutral processes are separately summarized.

Recent Developments in the Modelling of Heterogeneous Catalysts for CO2 Conversion to Chemicals

“…Carbon monoxide formed by RWGS reaction is a feedstock or key intermediate for the production of methanol, hydrocarbon fuels via FTS and a building block for carbonylation reactions . The RWGS reaction is endothermic (Table ) and thermodynamically favored at high temperatures with pressure‐independent chemical equilibrium and direct gas‐phase reaction which makes it one of the most promising high‐temperature chemical reactions …”

Photocarboxylation of Benzylic C–H Bonds

“…Obviously, utilization of CO 2 would provide an ideal, but challenging renewable one-carbon (C1) building block in organic synthesis. 1 In particular, one of these intriguing transformations of CO 2 is the carboxylation of carbon nucleophiles, offering a straightforward access to carboxylic acid derivatives. 2 Compared to using prefunctionalized starting materials, direct activation of C–H bonds and subsequent carboxylation represents an attractive and promising strategy for such CO 2 reactions as the number of steps to the target molecules is reduced, resulting in lower cost and less waste.…”

Photocatalytic Carboxylation of Phenyl Halides with CO2 by Metal‐Organic Frameworks Materials

“…Since the global warming problem becomes increasing serious, it is urgent to solve the problem of CO 2 that is the main origin of greenhouse gas. [ 1‐3 ] The use of CO 2 as a clean, cheap and abundant C1 building block, [ 4‐7 ] to couple it into organic reactions through the solar energy and produce high value added products, such as pharmaceutical intermediates and fine chemicals, is an primary choice in green chemistry. [ 8‐11 ] Among these intermediates, phenylpropionic acid compounds formed via the reaction of phenyl halides with CO 2 , such as ibuprofen, flurbiprofen, naproxen, ketoprofen, carbenicillin and diclofenac (Figure 1), play very important roles in medicinal chemistry because they are the basis of non‐steroidal anti‐inflammatory drugs (NSAIDs).…”