Initial exploration used the reaction of commercially available benzoyl fluoride 1, styrene 2 and phenylglyoxylic acid 3 (Table and With the optimized conditions in hand (Table , entry 1), the scope and limitations of this NHC/photoredox dual catalysed synthesis of 1,4-diketones was developed. Using benzoyl fluoride 1 and phenylglyoxylic acid 3 a variety of terminal alkene derivatives was explored in this process (Table ). Incorporation of halogenated (para-Br, para-F) as well as electron-withdrawing (para-CF3) substituents within the styrene component were tolerated, giving the desired 1,4diketones in 42-46% yield (7-9). Incorporation of the heteroaromatic 2-vinyl pyridine variant produced comparable yield of product (10). The incorporation of alkyl substituents at the para position were well tolerated (11-13), while ortho substitution (to give 14) or electron-donating (para-MeO) substituents delivered the 1,4-diketone (15) in lower yields. However, 15 could be obtained in an improved yield when using an Ir-based photocatalyst and changing reaction stoichiometries. Substrates that proved unsuccessful under the developed conditions included α-and ß-methyl styrene, 2-vinylthiophene, oct-1-ene and 4vinylpyridine. With the alkene scope established, attention turned to variation of the benzoyl fluoride component and the synthesis of unsymmetric 1,4-diketones (Table ). In each case ~5 % of the symmetrical 1,4-diketone product was also observed, likely formed through the same process as reported by Wu and co-workers. Trace amounts of the corresponding 1,2-dione, where effectively the styrene component has been excluded, were also detected. Larger π-systems such as biphenyl ( ) and 2-naphthyl (17) were well tolerated, although lower yields resulted from the use of 1-naphthyl (18), perhaps due to increased steric congestion. para-Fluoro- (19) and para-chloro-(20) substituted benzoyl fluorides worked well; however, para-bromo (21) and para-iodo (22) derivatives gave reduced product yield. However, 21 and 22 could be obtained in improved yields using alternative conditions with the Ir-based photocatalyst. Pleasingly, Given these promising results in terms of the breadth of both the alkene and benzoyl fluoride components, the scope of possible α-ketoacids was evaluated next.