The photolysis of electron-rich aryl nonaflates (ArONfs) in protic media was investigated and heterolysis of the Ar-OS bond (from 3 ArONf ) took place. The reaction generated a triplet phenyl cation that added to π-bond nucleophiles. This metal-free arylation method was made further useful by adopting in situ preparation of ArONf from the corresponding phenol.Scheme 1 Competitive Ar-OS vs. ArO-S bond photocleavage in aryl sulfonates. † Electronic supplementary information (ESI) available: Experimental details, copy of 1 H and 13 C NMR of 1a-1e, 6c, 7c, 8b,c, 10b, 10d, 10e and 11b.

The effect of surfactants (cationic, anionic, and nonionic) on the direct photochemistry of selected chlorophenol antimicrobials in aqueous solution has been investigated. The inclusion of the starting aromatics into micelles markedly directs the reaction towards a cleaner process (mainly photoreduction), contrasting with the variety of processes observed when the irradiation is carried out in neat water. This could have some implications from the environmental point of view because such paths may be significant in natural aquatic systems.

Metal-Free Arylations via Photochemical Activation of the Ar-OSO 2 R Bond in Aryl Nonaflates. -The reaction can be carried out using the premade ArOSO2Nf or the reagents can be made in situ. The presented approach represents the first generation of a phenyl cation starting directly from an electron-rich phenol. -(RAVIOLA, C.; CANEVARI, V.; PROTTI, S.; ALBINI, A.; FAGNONI*, M.; Green Chem. 15 (2013) 10, 2704-2708, http://dx.