One-Pot Amide\nSynthesis <i>via</i> a Shelf-Stable\nand Renewable C1 Transfer Reactant

4-Propylcatechol carbonate is a shelf-stable renewable\nC1 transfer\nreactant that is easily accessible <i>via</i> transesterification\nof dimethyl carbonate with 4-propylcatechol employing reactive distillation.\n4-Propylcatechol can be obtained from 4-propylguaiacol and dimethyl\ncarbonate from CO<sub>2</sub>. Both 4-propylguaiacol and dimethyl\ncarbonate are industrially produced on the multiton scale. The former\nis currently only accessible petrochemically but is expected to become\navailable on a large scale <i>via</i> future refinery of\nwood, based on reductive catalytic fractionation. A one-pot, two-step\nscalable synthesis of amides involving a selective ring opening of\n4-propylcatechol carbonate with Grignard reactants and subsequent\namidation of the <i>in situ</i>-formed catecholate ester\nintermediate with amines has been developed. The catecholate ester\nintermediates allow a fully controllable reactivity: less reactive\nin comparison to 4-propylcatechol carbonate in the ring opening step\nwith Grignard reactants and high reactivity in the reaction with amines\nin the amidation step due to neighboring group participation. No stoichiometric\nreagents or catalysts are required. The high selectivity of the one-pot\nprocess is reflected in the purification process. In most of the scope\nexamples, amides and the byproduct 4-propylcatechol can be separated\nthrough simple extractions, and no additional purification of amide\nis required. The 4-propylcatechol byproduct of the amide synthesis\ncan be easily recycled into a C1 transfer reactant.