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The development of new hydrogen-atom transfer (HAT) strategies within the framework of photoredox catalysis is highly appealing for its power to activate a desired C-H bond in the substrate leading to its selective functionalization. Reported here is the first photoredox-mediated hydrogen-atom transfer method for the efficient synthesis of ynones, ynamides, and ynoates with high regio- and chemoselectivity by direct functionalization of Csp2 (O)-H bonds. The broad synthetic application of this method has been demonstrated by the selective functionalization of C(O)-H bonds within complex molecular scaffolds., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, we disclose a strategy for the activation of N-(acyloxy)phthalimides towards photoinduced electron transfer through hydrogen bonding. This activation mode enables efficient access to C(sp 3 )-centered radicals upon decarboxylation from bench-stable and readily available substrates. Moreover, we demonstrate that the formed alkyl radicals can be successfully employed in a novel redox-neutral method for constructing sp 3 -sp 3 bonds across styrene moieties that gives straightforward access to complex alcohol and ether scaffolds., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)