The Versatile and Strategic -Carbamate Directed Metalation Group in the Synthesis of Aromatic Molecules: An Update.

The aryl -carbamate (ArOAm) group is among the strongest of the directed metalation groups (DMGs) in directed metalation (DM) chemistry, especially in the form Ar-OCONEt. Since the last comprehensive review of metalation chemistry involving ArOAms (published more than 30 years ago), the field has expanded significantly. For example, it now encompasses new substrates, solvent systems, and metalating agents, while conditions have been developed enabling metalation of ArOAm to be conducted in a green and sustainable manner. The ArOAm group has also proven to be effective in the anionic -Fries (AF) rearrangement, Directed remote metalation (DM), iterative DM sequences, and DM-halogen dance (HalD) synthetic strategies and has been transformed into a diverse range of functionalities and coupled with various groups through a range of cross-coupling (CC) strategies. Of ultimate value, the ArOAm group has demonstrated utility in the synthesis of a diverse range of bioactive and polycyclic aromatic compounds for various applications.