Photocatalytic aerobic benzylic C(sp3)−H oxygenations of aromatic hydrocarbons and C3‐substituted indoles were studied by employing a co‐catalytic system of 3DDQ* (DDQ=2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone) and tert‐butyl nitrite. The superior efficiency of these reaction conditions was demonstrated by comparison with the analogous thermal protocol, and a range of substrates could be oxidized catalytically and selectively in good yields.

A visible light-induced photocatalytic dehydrogenation/6π-cyclization/oxidation cascade converts 1-(nitromethyl)-2-aryl-1,2,3,4-tetrahydroisoquinolines into novel 12-nitro-substituted tetracyclic indolo[2,1-a]isoquinoline derivatives. Various photocatalysts promote the reaction in the presence of air and a base, the most efficient being 1-aminoanthraquinone in combination with K3 PO4 . Further, the 12-nitroindoloisoquinoline products can be accessed directly from C1-unfunctionalized 2-aryl-1,2,3,4-tetrahydroisoquinolines by extending the one-pot protocol with a foregoing photocatalytic cross-dehydrogenative coupling reaction, resulting in a quadruple cascade transformation.

Cross‐Dehydrogenative Coupling The photocatalytic C1‐functionalization of 2‐aryltetrahydroisoquinolines by cross‐dehydrogenative coupling with nitroalkanes is a well‐established method for the preparation of 1‐nitroalkyl‐2‐aryl‐tetrahydroisoquinolines. In their Communication on , M. Brasholz et al. describe that these primary coupling products readily undergo a subsequent oxidative cascade cyclization to furnish 12‐nitroindolo[2,1‐a]isoquinoline derivatives. Key to this hitherto unreported one‐pot transformation is the presence of a base, such as K3PO4 and aminoanthraquinones emerged as the ideal organic photocatalysts.

The Cover shows a visible light‐induced benzylic C(sp3)−H photooxygenation driven by the co‐catalytic system of triplet‐excited DDQ and nitric oxides, which are generated in situ from tert‐butyl nitrite and O2. In their Communication, F. Rusch et al. report that this photocatalytic protocol offers a dramatic increase of reaction rate relative to the thermal variant of the reaction, and a range of aromatic hydrocarbons and substituted indoles could be oxidized with good selectivity. Mechanistic control experiments suggest that benzylic cations are the key intermediates in the oxygenation reaction. More information can be found in the Communication by F. Rusch et al. on page 2881 in Issue 18, 2016 (DOI: 10.1002/cctc.201600704).

A photolytic aerobic oxidative cyclization of 1-nitromethyl substituted tetrahydroisoquinolines (I) and related pyridines (III) in the presence of 1-aminoanthraquinone as the catalyst is developed to yield condensed nitropyrrole derivatives. Combined with formation of the nitromethyl substrate from 2-aryltetrahydroisoquinolines and nitromethane a direct synthesis of products (IIa-d) is achieved using 1,5-diaminoanthraquinone as optimal catalyst. -(RUSCH, F.; UNKEL, L.-N.; ALPERS, D.; HOFFMANN, F.; BRASHOLZ*, M.; Chem. -Eur. J. 21 (2015) 23, 8336-8340, http://dx.doi.org/10.1002/chem.201500612 ; Inst. Org. Chem., Univ. Hamburg, D-20146 Hamburg, Germany; Eng.) -Mais 41-193