Insertion or Elimination of COx as C1 Building Blocks for Synthesizing Biorenewable Chemicals

ABSTRACT

Carbon oxides (COx, x = 1 or 2) are C1 building blocks that can be inserted into or eliminated from biomass‐derived platform molecules to produce renewable chemicals of industrial relevance. Introducing CO and CO ₂ via carbonylation and carboxylation reactions, respectively, extends the carbon skeleton and introduces oxygen‐containing functionalities in renewable chemicals. On the other hand, decarbonylation and decarboxylation reactions remove CO and CO ₂ , respectively, from biorenewable molecules, shortening the carbon skeleton, selectively deoxygenating, and introducing new functional groups. Platform chemicals derived from biomolecules have been transformed into high‐value organic compounds by strategically leveraging COx chemistry. These transformations are routinely carried out under catalytic conditions to ensure energy efficiency, reagent economy, waste minimization, and high selectivity and yield of the targeted product. In addition to conventional heating, the reactions are often performed under microwave irradiation, photolytic, and electrolytic conditions for better control of the reaction pathway and sustainability parameters. This review summarizes developments in this research area over the past two decades, highlights key accomplishments, identifies bottlenecks, and outlines avenues for future research.