Integration of CO₂ Reduction with Subsequent Carbonylation: Towards Extending Chemical Utilization of CO₂

Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO₂ , although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO₂ reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO₂ in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two-chamber reactor. Subsequently, palladium-catalyzed aminocarbonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)-mediated Pauson-Khand-type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cyclopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO₂ transformation.