Hydroformylation of specific substrates as a perspective route to monomers and valuable bifunctional compounds

Abstract

This review considers hydroformylation as a pivotal step in the synthesis of bifunctional molecules, the majority of which are critical monomers. The synthesis of bifunctional molecules via hydroformylation is only possible through the transformation of specific substrates (formaldehyde, lower epoxides, 1,3-butadiene, vinyl-, acryl-, allyl-, and oleic derivatives). Consequently, the catalysts utilized and the approaches to the reaction are unique and require a detailed study for each case. The review pays close attention to the distinctive features of these transformations for each group of substrates and undertakes a thorough analysis of the progress and achievements made, while also acknowledging the limitations. Additionally, the role of significant modern developments in the field of hydroformylation, which can also be applied as a powerful and versatile tool for the transformation of more complex substrates (potential monomer precursors), is emphasized. These include the development of new phosphorus-containing ligands for highly active and regioselective homogeneous systems, approaches to tandem transformations (isomerization-hydroformylation, reductive hydroformylation, hydroaminomethylation), and the design of new stable biphasic and heterogeneous systems for simplified catalyst recycling. The most significant advances are highlighted, which may serve for the development of more atom-efficient and environmentally friendly monomer synthesis processes using the hydroformylation step.