Moving away from unactivated alkenes, the protocol was then applied to a variety of functionalized styrenes (Fig. ). A selection of feedstock vinyl arenes decorated with both electron-donating and electron-withdrawing substituents afforded the desired difunctionalized products (2, 32-37 and 40-52) in generally high yields (> 70%) with no apparent preference for the electronic nature of the aryl substituent. Notably, highly electron-deficient pentafluoro styrene, also in combination with steric congestion as seen for 2,6-dichlorostyrene furnished the products 43 and 45 in high yields. To complement the amenable set of vinyl arenes, groups like benzyl chloride (49), TMS (50), carboxylic acid (51) and boronic acid (52) were well tolerated under the experimental conditions. Vinyl arene derivatives adorned with a substituent flanking the αor β-position of the styrene gave the desired products 53 and 54. Of note, β-chloroacylation of indene selectively provided the trans-isomer 56. β-chloroacylation of vinyl naphthalene provided compound 57 in 55% yield. However, vinyl pyridines showed no conversion under the standard reaction conditions, e.g. 58 could not be obtained. In the case of styrene derivatives bearing para-methoxy and α-phenyl groups, the corresponding dehydrochlorinated products (38, 39, and 55) could only be formed, which might be an indication for a change in mechanism, i.e. that for these substrates the oxidation of the radical intermediate of type II (Fig. ) to the cation III proceeds as opposed to delivering the chlorine via an intermediate IV (cf. Fig. ).