One-Pot Amide Synthesis <i>via</i> a Shelf-Stable and Renewable C1 Transfer Reactant

4-Propylcatechol carbonate is a shelf-stable renewable C1 transfer reactant that is easily accessible via transesterification of dimethyl carbonate with 4-propylcatechol employing reactive distillation. 4-Propylcatechol can be obtained from 4-propylguaiacol and dimethyl carbonate from CO2. Both 4-propylguaiacol and dimethyl carbonate are industrially produced on the multiton scale. The former is currently only accessible petrochemically but is expected to become available on a large scale via future refinery of wood, based on reductive catalytic fractionation. A one-pot, two-step scalable synthesis of amides involving a selective ring opening of 4-propylcatechol carbonate with Grignard reactants and subsequent amidation of the in situ-formed catecholate ester intermediate with amines has been developed. The catecholate ester intermediates allow a fully controllable reactivity: less reactive in comparison to 4-propylcatechol carbonate in the ring opening step with Grignard reactants and high reactivity in the reaction with amines in the amidation step due to neighboring group participation. No stoichiometric reagents or catalysts are required. The high selectivity of the one-pot process is reflected in the purification process. In most of the scope examples, amides and the byproduct 4-propylcatechol can be separated through simple extractions, and no additional purification of amide is required. The 4-propylcatechol byproduct of the amide synthesis can be easily recycled into a C1 transfer reactant.