Upon irradiation with visible light, the NiII complex 1 is converted to the reduced form 2 in the presence of NEt3. The Ni-based photosensitizer catalyzes the cyclization of a bromoalkyl-substituted indole.

Indoles and indazoles are common moieties in pharmaceuticals and naturally occurring bioactive compounds. The development of light-driven methods using earth-abundant transition-metal catalysts offers an attractive route for functionalization of such compounds. Herein, we report a visible-light-induced method for the C3- and N-alkylation of indoles and indazoles with styrenes, catalyzed by Co complexes based on the macrocyclic Mabiq ligand (Mabiq = 2–4:6–8-bis­(3,3,4,4-tetra­methyl­dihydro­pyrrolo)-10–15-(2,2′-biquinazolino)-[15]-1,3,5,8,10,14-hexaene-1,3,7,9,11,14-N6). The photochemical behavior of two CoIII catalysts was examined: Co­(Mabiq)­Cl2 and the newly synthesized Co­(MabiqBr)­Cl2, which contains the Br-modified ligand. Both complexes undergo visible-light-induced homolysis that is significant to their activity but exhibit differences in reactivity. The alkylation reactions are regioselective, furnishing the alkylated indole and indazole products in a Markovnikov fashion with excellent yields of up to 96% across a broad range of substrates. Notably, in contrast to dual-transition-metal and photoredox-catalyzed cross-coupling reactions, our studies reveal that the Co complex plays a dual roleas a photosensitizer and catalytically active metal center with the Mabiq ligand offering regiocontrol.

Starting from the respective tertiary α-silylmethyl amines, the intramolecular cyclization of α-aminoalkyl radicals to Michael acceptors produced tetrahydroisoquinolines. The reaction conditions included the use of 5 mol% of an iridium photoredox catalyst, dimethylformamide as the solvent, and equimolar amounts of water and cesium carbonate as the additives. 13 substrates were synthesized from ortho-alkylbenzaldehydes in a three-step procedure involving a carbonyl condensation, a radical bromination, and a substitution by a secondary α-silylmethyl amine. After optimization of the photocyclization, the reaction delivered tetrahydroisoquinolines in moderate to high yields (41–83%). A facial diastereoselectivity (dr ≅ 80:20) was observed with chiral substrates and a crystal structure provided evidence for the relative configuration of the major diastereoisomer. A catalytic cycle with direct electron transfer to the photoexcited metal catalyst is proposed.