Unprecedented selective homogeneous cobalt-catalysed reductive alkoxylation of cyclic imides under mild conditionsElectronic supplementary information (ESI) available: General information concerning experimental procedures, additional tables, figures, schemes, characterization data and NMR spectra of the isolated compounds are available. See DOI: 10.1039/c7sc01175j

The first general and efficient non-noble metal-catalysed reductive C2-alkoxylation of cyclic imides (phthalimides and succinimides) is presented. Crucial for the success is the use of [Co(BF 4 ) 2 ·6H 2 O/triphos ( L1 )] combination and no external additives are required. Using the optimal cobalt-system, the hydrogenation of the aromatic ring of the parent phthalimide is avoided and only one of the carbonyl groups is selectively functionalized. The resulting products, N - and aryl-ring substituted 3-alkoxy-2,3-dihydro-1 H -isoindolin-1-one and N -substituted 3-alkoxy-pyrrolidin-2-one derivatives, are prepared under mild conditions in good to excellent isolated yields. Intramolecular reductive couplings can also be performed affording tricyclic compounds in a one-step process. The present protocol opens the way to the development of new base-metal processes for the straightforward synthesis of functionalized N -heterocyclic compounds of pharmaceutical and biological interest. The first general and efficient non-noble metal-catalysed reductive C2-alkoxylation of cyclic imides (phthalimides and succinimides) is presented. Crucial for the success is the use of [Co(BF 4 ) 2 ·6H 2 O/triphos ( L1 )] combination and no external additives are required.