The development of synthetic methodologies to produce 1,4-diketones is a well-studied area of research, in large part due to their utility as precursors of various heterocycles such as furans, thiophenes, and pyrroles. While a number of disconnections are possible, perhaps the most commonly used synthetic strategy follows the umpolung approach of disconnecting the 1,4-diketone into a nucleophilic acyl group equivalent and an α,ß-unsaturated ketone, such as employed in the Stetter reaction. The Stetter reaction uses substoichiometric amounts of an N-heterocyclic carbene (NHC) in the presence of an aldehyde and an α,ß-unsaturated ketone to furnish the desired 1,4diketones via a nucleophilic Breslow intermediate. Another possible disconnection would involve generating the 1,4-diketone from three distinct fragments. While such processes have been developed employing conventional two electron mechanisms, they are currently limited to the use of 1,3-diketones in combination with an appropriate α-ketoaldehyde. As a more general approach, the 1,4-diketone may be disconnected into two acyl radical components and an alkene, which in the forward direction would involve a radical addition of one acyl group to the alkene, followed by a subsequent radical-radical coupling. This strategy has been executed successfully by the groups of Ackermann, 9 Gilmour, 10 Larionov, Li, and Wu. However, these examples are either limited to only symmetric 1,4-diketones or are restricted in terms of the scope of the acyl radical or alkenes available. The challenge of making unsymmetric 1,4-diketones using this strategy is significant, as the two acyl radicals must offer distinct reactivity to avoid forming a mixture of symmetric and unsymmetric products. Acyl radical generation and subsequent addition to alkenes using photoredox catalysis from commercially available, or simple to prepare, α-ketoacids, is wellknown. Application to achieve selective formation of the desired unsymmetric 1,4diketones requires another acyl radical, or equivalent, that must be generated simultaneously but itself will not react with the alkene. In a recent report Wang and Ackermann accomplished this transformation selectively through the use of metallaphotoredox catalysis using a tungsten polyoxometalate photocatalyst and a nickel co-catalyst. As an alternative, we envisaged that an acyl azolium intermediate, generated from an NHC catalyst and an appropriate electrophile, could undergo reduction through single electron transfer (SET) to the corresponding NHC-stabilised ketyl radical, which could act as the second acyl radical required for this transformation. During the course of our investigations Feng et al. published the use of triphenylphosphine in combination with NHC/photoredox dual catalysis using an iridium(III) photocatalyst for the generation of acyl radicals from benzoic acids generated in situ. However, to achieve the challenging synthesis of unsymmetric Scheme 1. (A) Previous work using stoichiometric imidazolium species.