Following the report of our original dual catalytic azido-arylation work , and during the studies detailed here, Ritter and co-workers drew on a very similar design hypothesis to underpin a Meerweintype aryl-bromination process (Scheme 1) 19 , which exploited photocatalytic reduction of arylthianthrenium salts to generate aryl radical species. Subsequent addition to an alkene forms a homobenzylic radical. Reduction of the oxidized photocatalytic species by bromide ion gives rise to bromine radical, which quickly combines with the homobenzylic radical to form the C-Br bond. As the turnover step in this catalytic system relies on oxidation of an anion to a radical, it may be restricted to the use of more 'oxidizable' nucleophiles, potentially limiting wider application. For example, the corresponding reaction with a chloride ion is seemingly out of range of this delicately balanced photocatalytic (E1/2[Cl•/Cl -] = +1.36 V vs SCE compared with E1/2 [Br•/Br -] = +0.83 V vs SCE and E1/2 [PTH• + /PTH] = +0.90 V vs SCE) 20 . Additionally, the carbon-bromide bond formation proceeds through a radical combination reaction, which will make catalysis of this step difficult to envisage . With optimal reaction conditions in hand for the dual catalytic alkene aryl-chlorination, the scope of this new transformation was first evaluated using a selection of styrenes. Pleasingly, a range substituted styrenes could be accommodated. When using a catalyst combination of [Cu(I)(dpp)2](PF6) and [(bpmen)Fe(II)Cl2], a range of electronically and sterically diverse substituted styrenes (3a-j) were found to work well (Figure ). Notable examples include the accommodation of readily reducible nitroarenes in the reaction manifold, with the reaction exclusively leading to the desired alkyl chloride 3i. Styrenes containing Lewis-basic heteroatoms, such as 2vinyl pyridine showed good compatibility to the aryl-chlorination producing the desired product in 70% yield (3k). In contrast, the aryl-chlorination product derived from 2-vinyl thiophene (not shown) was susceptible to facile elimination (see supporting information, scheme S2). Meerwein-type aryl-chlorination is rarely successful with non-activated alkenes due to a slow aryl radical addition step. Interestingly, a reaction with a Cu(I)-photocatalyst and Cugroup-transfer catalyst gave a modest conversion to product of 27% assay yield, whereas a reaction with the Cu(I)-photocatalyst and Fe(II)-group-transfer catalyst gave the desired aryl-chlorination product 3au in an improved yield of 40%. The higher efficiency of Fe-group-transfer catalyst promoting aryl-chlorination of non-activated alkenes or styrenes may attribute to the hypothesis that the partial positive charge generated during the Fe-mediated chlorine atom-transfer can be stabilized by the electron-donating effects of neighboring alkyl or aryl groups while such effect can only weaken the stability of the partial negative charge accumulated in Cu-mediated chlorine atom-transfer. Further examples of non-activated alkenes include the reactions of methylenecyclobutane and N-Cbzmethylenepiperidine (to produce β-aryl-azidoalkanes bearing quaternary α-center (3l, 3m) in reasonable yield. The reaction with remotely functionalized linear alkenes (3n-3r), including hydroxyl, halide and ester motifs, also provided the desired products in synthetically useful yields. Oxygenated functionalities, such as acetal (3s) and diester (3t), also produce useful yields of products. Among all the non-activated alkenes evaluated, those bearing remote ester functionalities led to higher yields of the desired aryl-chlorination adducts (3r, 3t), which may result from a long-range directing effect on the Fe-based transfer catalyst . The successful accommodation of non-activated alkenes in our dual catalytic aryl-chlorination reaction sets this process apart from other Meerwein-type variants .