Selective Ruthenium-Catalyzed Reductive Alkoxylation and Amination of Cyclic Imides

Reported herein, for the first time, is the selective ruthenium‐catalyzed reductive alkoxylation and amination of phthalimides/succinimides. Notably, this novel methodology avoids hydrogenation of the aromatic ring and allows methoxylation of substituted imides with good to excellent selectivity for one of the carbonyl groups. The reported method opens the door to the development of new processes for the selective synthesis of various functionalized N‐heterocyclic compounds. As an example, intramolecular reductive couplings to afford tricyclic compounds are presented for the first time. Valorization of imides: Novel catalytic hydrogenations of imides proceed in high yields under comparably mild reaction conditions (see scheme). In the case of aryl‐ring‐substituted derivatives, notable regioselective transformations are achieved for the first time.