Strategic Utilization of Multifunctional Carbene for Direct Synthesis of Carboxylic–Phosphinic Mixed Anhydride from CO2

Direct synthesis of carboxylic–phosphinic mixed anhydrides has been achieved by treating carbon dioxide with N‐phosphine oxide‐substituted imidazolylidenes (PoxIms) that contain both nucleophilic carbene and electrophilic phosphorus moieties. This novel mixed anhydride was efficiently derivatized into an ester, an amide, and an unsymmetrical ketone via transformation into its corresponding imidazolium salt followed by a dual substitution reaction. The presented work used well‐designed multifunctional carbene reagents to establish a novel utility for carbon dioxide in organic synthesis.